CN1867657A - Composition for protection of glassware in dishwashers - Google Patents
Composition for protection of glassware in dishwashers Download PDFInfo
- Publication number
- CN1867657A CN1867657A CNA2004800306261A CN200480030626A CN1867657A CN 1867657 A CN1867657 A CN 1867657A CN A2004800306261 A CNA2004800306261 A CN A2004800306261A CN 200480030626 A CN200480030626 A CN 200480030626A CN 1867657 A CN1867657 A CN 1867657A
- Authority
- CN
- China
- Prior art keywords
- composition
- bismuth
- zinc
- weight
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 83
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000004411 aluminium Substances 0.000 claims abstract description 75
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 61
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011701 zinc Substances 0.000 claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000004851 dishwashing Methods 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims description 101
- 230000007797 corrosion Effects 0.000 claims description 44
- 238000005260 corrosion Methods 0.000 claims description 44
- 230000004087 circulation Effects 0.000 claims description 43
- 239000003599 detergent Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 39
- 230000000694 effects Effects 0.000 claims description 33
- 238000009472 formulation Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- -1 vitriol Chemical class 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001152 Bi alloy Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910001297 Zn alloy Inorganic materials 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 230000001627 detrimental effect Effects 0.000 abstract 1
- 238000005034 decoration Methods 0.000 description 36
- 239000008186 active pharmaceutical agent Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 230000006378 damage Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 240000002234 Allium sativum Species 0.000 description 8
- 235000004611 garlic Nutrition 0.000 description 8
- 239000003826 tablet Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000000996 additive effect Effects 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
- 230000001681 protective effect Effects 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 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 3
- 208000014674 injury Diseases 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005355 lead glass Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007916 tablet composition Substances 0.000 description 3
- 239000004246 zinc acetate Substances 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
- 102000035195 Peptidases Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 208000001848 dysentery Diseases 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 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
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001777 Tupperware Polymers 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000009525 mild injury Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
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
Technical field
The present invention relates to a kind of composition, said composition comprises zinc and bismuth, is used for preventing the unfavorable phenomenon that glassware particularly takes place owing to the existence of aluminium at the automatic tableware washing process.
Background technology
To be subjected to the corrosive problem be known to glassware in the automatic tableware washing process.The etching problem that has proposed glassware is because the result of two kinds of different phenomenons.A kind of suggestion thinks that described corrosion is that mineral substance releases owing to be accompanied by the hydrolysis of silicate network from glass network.Another kind of suggestion is thought because silicate material disengages from glass.
After a plurality of independently cycles of washing, these phenomenons can cause damage to glassware.This infringement can comprise turbidization, scratch, dragging article (streaks) and other variable color/disadvantageous effect.
Having proposed silicate material can avoid each material to disengage from glass composition effectively.Yet, use silicate compound may have disadvantageous side effect, for example have the isolating tendency of silicate material that promotes glass surface.
Another kind of solution is to use the zinc (for example United States Patent (USP) 3,677, and 820 is described) of metallic forms or the zinc of compound form.For example at United States Patent (USP) 3,255, described in 117 and used soluble zinc compound to prevent glassware corrosion in the dish-washing machine.
Found to use the glass and the pottery that contain zinc can solve glassware corrosive problem in the dish-washing machine.WO-A-01/64823 has described in the automatic tableware washing process to use and has contained the zinc ceramic composition and come the protective glass vessel.GB-A-2372500 and WO-A-00/39259 have described and have used the soluble glass composition that contains zinc (existing with ionic species) to come the protective glass vessel in the automatic tableware washing process.Use zinciferous ceramic/glass composition effectively overcoming above-mentioned low solubility/sedimentary problem in the protective glass vessel.
Yet the problem relevant with zinciferous ceramic/glass composition (and water-soluble/insoluble zn cpds) also has, and these compositions do not have gratifying performance in the corrosion of the glassware that prevents to have decoration.
Bismuth has been used as the corrosion that additive helps prevent the glazing glassware.For example, BE860180 has described and has used bismuth to avoid the infringement that the glazing utensil that has decoration is caused.Yet,, make the value of bismuth in this purpose be subjected to impairment owing to use bismuth compound to the disadvantageous effect that other component caused in the washing process.In this respect, found that bismuth can make plastic material (for example Tupperware ) painted.Bismuth also makes the glassware and the tableware that do not have decoration form brown spot.In addition, although the glazing of glassware part can be protected, found that bismuth can make non-enamel part painted.Owing to these reasons, avoided using bismuth as the enamel protective material.
When cleaning glass vessel in dish-washing machine, also may run into other problem and be, the problem that causes because of the existence of aluminium in the dish-washing machine, automatic dishwashing detergent manufacturers still can not address this problem.
In the past, in for example United States Patent (USP) 3,255,117 and WO-A-96/36687, propose the glass corrosion inhibitor of aluminium as meticulous tableware (for example lead crystal glass).
Yet also have a query for whether in full force and effect aluminium in this a kind of target: though when repeated washing glass in the automatic tableware washing machine, observe and can reduce mass loss and streak (cordlines), turbidization of glass but aggravated.
In addition, use the subject matter of aluminium to be, because the use of aluminium, glassware can produce iris.Consequently, it is chromatic clear, colorless glass to be changed into.In fact, found that aluminium is very serious in this unfavorable effect on the one hand, to such an extent as to, also can observe this effect even in dishwashing detergent liquid, there is the aluminium of minute quantity.For example, in dish washing detergent, avoid using dyestuff,, also will avoid the use of this dyestuff, in order to avoid produce rainbow effect even the amount of the aluminium that described dyestuff needs is extremely low based on aluminium.
This disadvantageous effect in glassware is obvious inhumanly is willing to.Therefore in automatic dishwashing detergent, must avoid the existence of aluminium.Yet, though can control aluminium content in the washing composition (and automatic tableware washing machine), and usually that its maintenance is low as far as possible, and human consumer's behavior still may cause glassware to contact with aluminium.If for example the user washs aluminum products (for example normal domestic use garlic press (garlic press)) in the automatic tableware washing machine, this situation still may take place.In this case, the aluminium that is discharged in the dishwashing detergent liquid is enough to cause above-mentioned disadvantageous effect.Even this effect is also clearly after single cycles of washing.If when the user washs such as other aluminum products such as some prefabricated foodstuff containers, can see described effect equally in dish-washing machine.If dish-washing machine comprises the aluminium assembly (for example screw or sieve) of any exposure, also may cause described effect.
Because dishwashing detergent liquid is generally alkalescence, and aluminium dissolves enhancing under high pH, therefore in dish-washing machine, cause the metallic aluminium problems of dissolution of iris problem especially outstanding.
Another disadvantageous effect of relevant use aluminium is that known aluminium can aggravate the turbidization corrosion of glass.This is opposite to the active effect that mass loss and streak are produced with aluminium.Obviously, this unfavorable effect has surpassed any active effect, therefore will avoid.
Summary of the invention
The objective of the invention is to avoid/alleviate the problems referred to above.
A first aspect of the present invention provides a kind of composition, and said composition contains zinc and bismuth, is used for the disadvantageous effect that prevents that glassware is subjected to owing to contact aluminium at the automatic tableware washing process.
Should be appreciated that described composition is to be used for solving because of glassware contacting the potential problems that may cause at dishwashing detergent liquid with the aluminium source.
In the present invention, glassware one speech is construed as and comprises the article of being made by glass (for example drinking glass and dish), and it can be (for example has enamel and/or have etched pattern/glass additive) that has decoration.Glassware one speech will also be understood that these class vessel can comprise the material (for example pottery) except that glass, and have glass/enamel coating or decoration (for example glazed ceramic disc) in order to comprise other household utensil.
Found that in the automatic tableware washing process disadvantageous effect (for example iris) aspect that prevents because of existing aluminium to cause in the dishwashing detergent liquid that is combined in of zinc and bismuth has very favorable character.In addition, also highly beneficial in the protection that is applied in the simple glass vessel of said composition, find that also described composition is very beneficial for the protection of glazing glassware/pottery.Therefore, for the glassware/pottery that has decoration with do not have the glassware of decoration, can adopt independent composition that the corrosion prevention of glassware in dish-washing machine is provided now, and solve the problem that the existence owing to aluminium produces.
The used zinc and the ratio of bismuth are 1: 100～100: 1 (in the quality of described metal) in the preferred described composition.More preferably the ratio of zinc and bismuth is 1: 10～10: 1 in mass in described composition, more preferably 1: 5～5: 1, most preferably is about 1: 1.
According to aforementioned proportion, provide the zinc to the dish-washing machine circulation and the amount of bismuth to be preferably 1mg～1000mg, more preferably 1mg～500mg, more preferably 1mg～200mg, more preferably 5mg～100mg.Preferred described weight is the combination weight of two kinds of described metals.
Most preferably zinc and bismuth obtain as ion in the washings of dish-washing machine.
Zinc and bismuth can provide ion to dishwashing detergent liquid with any suitable form.
An example of appropriate form is to use the metallic forms of described metal.This form can be used as the absolute version of each metal that is placed in the dish-washing machine.Found that this form is dissolved and the soluble ion of bismuth and zinc is provided in a plurality of cycles of washing.Metallic forms can also comprise the mixture (for example alloy) of zinc and bismuth.This alloy can also comprise other element, for example for guaranteeing necessary other metallic element of stability/solvability of this alloy.
The preferred physical form of metal/alloy comprises sheet, fiber, particle, powder, piece (for example cubes) or their mixture in sheet, crack with holes.
Another example of appropriate form is to use the salt or the compound of bismuth and/or zinc.Thereby most preferably described salt/compound is to have salt/compound that suitable solubleness can be observed the effect of zinc and bismuth in washings.Yet, also can use the salt of the above-mentioned arbitrary element that only has low solubility.In latter event (when using the metallic forms of one or more elements itself), the usage quantity of salt/compound can correspondingly increase in dish-washing machine, with the low solubility of compensation low solubility salt.
Most preferably described salt/compound does not contain dish-washing machine/dish-washing machine content is had the component of corrodibility and disadvantageous effect.In described salt/compound was ionic situation, preferred described salt/compound did not contain the known cl anion that dish-washing machine (more specifically, to stainless steel tableware washing machine assembly/tableware) is had disadvantageous effect.
The preferred example of suitable metal-salt comprises having following anionic compound: such as nitrate radical, sulfate radical, halide anion (particularly fluorion), phosphate radical (solubility), carbonate and carboxylate radical (for example from C
1～C
10The anion of carboxylic acid with mono carboxylic or many carboxyl functionalities, especially acetate moiety and citrate).
Preferred example with metallic compound of low solubility comprises the oxide compound of described metal.
Can adopt the mixture of multiple compound.Can also adopt the different compounds of every kind of metal.
Most preferably described salt/compound is the part of detergent formulations.This detergent formulations can comprise rinse aid.
Described detergent formulations can be a detergent formulations commonly used arbitrarily, and it can be the type that dish-washing machine adopts usually.Said preparation can comprise liquid, gel, powder or tablet.When said preparation was liquid/gel, zinc and bismuth were present in the interior solution of liquid/gel usually.Yet, also can consider to make zinc and bismuth to be present in the liquid/gel, thereby make zinc and bismuth can comprise suspended particle (" spot " for example, in these preparations, seen usually) with the form of insoluble salt/compound.
Described detergent formulations contains other component of often seeing usually in the dishwashing detergent agent formulation.At this on the one hand, detergent formulations generally contains one or more components that is selected from tensio-active agent (non-ionic, anionic, cationic and zwitterionic), washing assistant, enzyme, froth suppressor, SYNTHETIC OPTICAL WHITNER, bleach activator, thickening material, perfume compound and dyestuff etc.
Most preferably when zinc and bismuth were present in the dishwashing detergent agent formulation simultaneously, described metal accounted for the 0.002 weight %～6 weight % (in the weight of these two kinds of metals) of this detergent formulations.More preferably described metal accounts for the 0.01 weight %～3 weight % of this detergent formulations, most preferably is 0.02 weight %～1.3 weight % (for example being 0.4 weight % in the tablet of 20g).
In the situation of rinse aid, particularly when rinse aid be that preferred described metal accounts for the 0.03 weight %～30 weight % (in the weight of these two kinds of metals) of this rinse aid preparation when being used for unique source of the bismuth of dish-washing machine and zinc.More preferably described metal accounts for the 0.15 weight %～15 weight % of this rinse aid preparation, most preferably accounts for 0.3 weight %～7 weight %.
Zinc and/or bismuth can also exist with solubility ceramic/glass preparation.Described glass/ceramic can comprise such as silicon-dioxide (SiO
2) or boron oxide compound (B for example
2O
3), basic metal/alkaline earth metal oxide (Na for example
2O, K
2O, CaO) and/or phosphorous oxides (P for example
2O
5) wait glass to form material.
Described glass/ceramic can comprise homogeneous mass, perhaps alternatively, described glass/ceramic can be what to grind/pulverize.When described glass/ceramic be what to grind/pulverize the time, its particle diameter preferably is lower than 500 μ m.
Will also be appreciated that zinc and bismuth, the multi-form mixture that can use each metal to exist with different physical form for above-mentioned form of ownership.
At this on the one hand, one of also can described metal exist, and another kind of metal may reside in washing composition/rinse aid preparation with the form of additive.As an example, zinc can be present in described washing composition/rinse aid with one or more other detergent components, adds and bismuth can be used as independent additive (for example being placed on the glass composition in the dish-washing machine).Obviously, according to the present invention, other combination of physical form can be satisfied makes bismuth and zinc all can be provided to requirement in the washings.
Surprisingly, when also finding in the combination with bismuth and zinc solves because of dishwashing detergent liquid, to exist the problem that aluminium causes, not only eliminate the disadvantageous effect that aluminium causes, but also strengthened bismuth and the zinc positively effect in the corrosion that prevents to have glassware decoration and that do not have decoration.
Therefore, a second aspect of the present invention provides the composition that contains zinc, bismuth and aluminium, and said composition is used for protecting the glassware of automatic tableware washing machine.
Surprisingly, when the repeated washing circulation time that said composition is used for the automatic tableware washing machine, the disadvantageous effect of turbidization of glass that the existence of seeing in the past owing to aluminium causes has reduced greatly.
Should be appreciated that the feature of first aspect present invention also is applicable to a second aspect of the present invention through suitable change.
In described composition, can there be (for example, metallic forms, complete/partly soluble aluminium salt/organic compound) with arbitrary form in aluminium.The preferred existence of aluminium in preparation makes each cycles of washing can discharge the aluminium of 5mg～200mg.
In addition; found when with the combination of zinc and bismuth with solving in the dish-washing machine when having the problem that aluminum ion causes; if this composition is used in combination with silicate source; just can prevent to obtain identical effect aspect the glass corrosion, and significantly strengthen being opposite to the protection of the aluminum products corrosion (problem of generally finding in the past) in the dish-washing machine.
Therefore, a third aspect of the present invention provides the composition that contains zinc, bismuth and silicate, and said composition is used for protecting the aluminum products of automatic tableware washing machine.
Surprisingly, when the repeated washing circulation time that said composition is used for the automatic tableware washing machine, the aluminium corrosive adverse events of seeing has in the past reduced greatly.
Should be appreciated that the feature of first aspect present invention also is applicable to a third aspect of the present invention through suitable change.
With respect to the weight of zinc and bismuth component, the ratio of the preferred existing amount of silicate is up to 1000: 1 (weight one speech is meant in the weight that comprises element itself described in any compound/mixture of described element).More preferably the amount of silicate is, silicate is up to 500: 1 with the ratio of zinc and bismuth, most preferably is up to 100: 1.
Can there be (for example complete/partly soluble salt, organic compound (for example silicone), water-soluble glass or pottery) with arbitrary form in described silicate in composition.
Described silicate preferred package containing metal oxide compound (for example, alkalimetal oxide, for example Na
2O or K
2O) with silicon-dioxide (SiO
2) mixture.The ratio of preferred silicate and metal oxide is 1.0～4.0.The preferred example of silicate is metal (for example basic metal) bisilicate, such as Na
2Si
2O
5(ratio of metal oxide and silicon-dioxide is 2.0).
Now by the present invention further being described with reference to following non-limiting example.
Embodiment
Glassware corrosion embodiment
In the present embodiment, following detergent composition (shown in table GL 1a) is used as basic detergent formulations.Said preparation uses with tablet form.
Table GL 1a
| Component | ％ |
| Tripoly phosphate sodium STPP | 45.0 |
| Sodium bicarbonate | 2.0 |
| Yellow soda ash | 18.5 |
| Sodium peroxoborate | 10.0 |
| TAED (tetraacetyl ethylene diamine) | 2.5 |
| Proteolytic enzyme | 1.5 |
| Amylase | 0.5 |
| Nonionogenic tenside | 3.5 |
| Polyoxyethylene glycol | 7.5 |
| Perfume compound+dyestuff | 0.3 |
| Assistant agent | Surplus |
In the present embodiment, with the source (as table GL 1b shown in) of following glass composition as zinc and bismuth.Used glass preparation is that solid form (is of a size of 4cm * 1cm * 1cm)
Table GL 1b
| Component | ％ |
| P 2O 5 | 60.0 |
| K 2O | 20.3 |
| Bi 2O 3 | 3.2(2.86％Bi) |
| B 2O 3 | 1.3 |
| CaO | 1.0 |
| ZnO | 14.2(11.4％Zn) |
When using according to following method, the mass loss average out to 0.35g/ circulation of glass block is equivalent to 10mg Bi
3+/ circulation and 40mg Zn
2+/ circulation.
Testing method
In the present embodiment, washing test glass cylinder 50 times～100 times in special durability test dish-washing machine (Miele G 541 Special).
The dosage that cleans: the above-mentioned basic detergent tablet of 20g uses with other additives (as specifying in the present embodiment).When the beginning of clean cycle, throw in described tablet automatically.
Water hardness in the machine: be lower than 0.5dGH, concentrate by ion-exchanger and soften, do not move inner ion-exchanger.
65 ℃ of wash procedures (cleaning and rinse cycle are all 65 ℃ of operations).
The water yield of each cycle consumption: 23.5 liters.
The glassware of being tested does not pollute.
Test report comprises following glass cylinder type:
Transparent glass cylinder
Luigi Bormoli (Italy):
" linea Michelangelo David " C32 white wine glass cylinder 19cl.
Arc-International (France):
" Luminarc Octime Transparent ", whisky glass cylinder 30cl.
" Longchamp ", 17cl, goblet, lead crystal glass (lead crystal glass).
" Arcoroc Elegance ", grape wine glass cylinder, 14.5cl.
Ruhr Kristall Glas (Germany):
" K lner Stange ", 24cl, beer glass.
" RKG Bier ", beer goblet, 38cl.
Nachtmann Bleikristallwerke (Germany):
" Longdrink-glass ", special (dish-washing machine sensitivity) is the ray c. mark the iii manufacturing specially.
The glassware that has decoration
Ruhr Kristall Glas (Germany):
“Snoopy Look In”，Longdrink Nordland 28cl。
“Teddy”，Primusbecher 16cl。
Arc-International (France):
" Kenia ", service plate, 19.5cm.
After 50 times～100 times test washings, by the gravimetric loss of gravimetry.(iris) or assessment glass surface visible variation in special lamp box (turbidization of glass, knife-line corrosion (line corrosion) and decoration infringement) in natural light.The size of lamp box is 70cm * 40cm * 65cm (length * wide * height), and unglazed black is painted in the inside of case.Lamp box is thrown light on from the top with L 20w/25S (60cm long) tengsten lamp, cover front portion at tengsten lamp with covert.Shelf is placed in the case, and glass cylinder is placed on the shelf to assess.Case is opening forwardly.
Use following standard that glass corrosion is assessed: turbidization of glass (GC), infringement (DS) and iris (IR) are decorated in knife-line corrosion (CL).According to following table each parameter is given a mark.
| Assessment | The infringement situation |
| 0 | Glass cylinder is infringement not |
| 1 | A first minor damage/almost can't see |
| 2 | Mild damage, expert can see or can see in lamp box |
| 3 | Visible damage |
| 4 | Grievous injury, obviously as seen |
Comparative example 1
In this comparative example, only use basic detergent formulations.
Test result is shown in table GL 2a (glass corrosion) and table GL 2b (mass loss).
Table GL 2a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||||||
| 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 Klsch | 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 | ||
| On average | 2.29 | 2.71 | 0.0 | 2.93 | 3.43 | 0.0 | ||
| The glassware that has decoration | DS | IR | DS | IR | ||||
| Snoopy | 3.0 | - | 3.5 | - | ||||
| Teddy | 3.5 | - | 4.0 | - | ||||
| The Kenia service plate | 3.5 | 0.0 | 4.0 | 0.0 | ||||
| On average | 3.33 | - | 3.83 | - | ||||
Table GL 2b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 35 | 59 |
| Octime | 25 | 48 |
| Longchamp | 58 | 94 |
| RKG Klsch | 24.5 | 45.5 |
| RKG Bier | 40 | 72 |
| Nachtmann Longdrink | 70 | 124 |
| Arcoroc Elegance | 17 | 30 |
| Add up to | 269.5 | 472.5 |
| The glassware that has decoration | ||
| Snoopy | 223 | 502 |
| Teddy | 67 | 145 |
| The Kenia service plate | 110 | 230 |
| Add up to | 400 | 877 |
Comparative example 2
In this comparative example, only use basic washing composition.Also has aluminium matter garlic press in addition in the dish-washing machine.
Test result is shown in table GL 3a (glass corrosion) and table GL 3b (mass loss).
Table GL 3a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||||||
| 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 Klsch | 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 | ||
| On average | 2.36 | 1.29 | 2.5 | 3.79 | 3.07 | 2.81 | ||
| The glassware that has decoration | DS | IR | DS | IR | ||||
| Snoopy | 2.5 | - | 3.5 | - | ||||
| Teddy | 2.5 | - | 3.5 | - | ||||
| The Kenia service plate | 3.0 | 3.0 | 3.5 | 3.0 | ||||
| On average | 2.67 | - | 3.5 | - | ||||
Table GL 3b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 8 | 25 |
| Octime | 5.5 | 12.5 |
| Longchamp | 21 | 49 |
| RKG Klsch | 6 | 13 |
| RKG Bier | 23 | 53 |
| Nachtmann Longdrink | 24 | 55 |
| Arcoroc Elegance | 7 | 14 |
| Add up to | 94.5 | 221 |
| The glassware that has decoration | ||
| Snoopy | 77 | 181 |
| Teddy | 16 | 46 |
| The Kenia service plate | 35 | 93 |
| Add up to | 128 | 320 |
Comparative example 1 and 2 shows; though aluminium can provide mass loss/knife-line corrosion protection for having the glassware of decorating and not having a decoration, it makes and has glassware decoration and that do not have decoration produce rainbow effect (when existing with metallic forms as garlic press) in dishwashing detergent liquid.Aluminium also aggravated glass turbidization corrosion-this is particularly evident after 100 cycles of washing.
Embodiment 1
In the present embodiment, except basic detergent tablet, also use the glass of bismuth-containing and zinc.
In dish-washing machine, also there is aluminium matter garlic press.
The result is shown in table GL 4 (iris).
Table GL 4-iris
| Glass cylinder | 50 circulations | 100 circulations |
| IR | IR | |
| Michelangelo | 0.0 | 0.0 |
| Octime | 0.0 | 0.0 |
| Longchamp | 0.0 | 0.0 |
| RKG Klsch | 0.0 | 0.0 |
| RKG Bier | 0.0 | 0.0 |
| Nachtmann Longdrink | 0.0 | 0.0 |
| Arcoroc Elegance | 0.0 | 0.0 |
| On average | 0.0 | 0.0 |
| The glassware that has decoration | IR | IR |
| Snoopy | - | - |
| Teddy | - | - |
| The Kenia service plate | 0.0 | 0.0 |
| On average | - | - |
The result of embodiment 1 shows, eliminated the iridescent disadvantageous effect that the existence because of aluminium causes when having bismuth and zinc simultaneously fully.
Embodiment 2
In the present embodiment, except basic detergent tablet, also use the glass of bismuth-containing and zinc.
In dish-washing machine, also there is aluminium matter garlic press (yet, ask for an interview next section).
Test result is shown in table GL 5a (glass corrosion) and table GL 5b (mass loss).In these tables, do not obtain when data presented has aluminium in the bracket-by having only detergent formulations and bismuth and zinc water-soluble glass piece to obtain.Other data presentation the result who obtains when having aluminium matter garlic press.
Table GL 5a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||
| 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 Klsch | 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) |
| On average | 1.07 (1.57) | 0.79 (0.93) | 2.0 (2.50) | 1.29 (2.14) |
| The glassware that has decoration | DS | DS | ||
| Snoopy | 1.0(1.5) | 2.0(2.5) | ||
| Teddy | 1.5(2.0) | 2.5(2.5) | ||
| The Kenia service plate | 1.0(2.0) | 2.0(3.0) | ||
| On average | 1.17(1.83) | 2.17(2.67) | ||
Table GL 5b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 3.0(11) | (25) |
| Octime | 0.0(14.5) | (20.5) |
| Longchamp | 3.0(19) | (30) |
| RKG Klsch | 2.0(9.5) | (18.5) |
| RKG Bier | 5.0(13) | (26) |
| Nachtmann Longdrink | 0.0(26) | (34) |
| Arcoroc Elegance | 2.0(9) | (14) |
| Add up to | 15.0(102) | (168) |
| The glassware that has decoration | ||
| Snoopy | 7.0(62) | 21.0(121) |
| Teddy | 6.0(24) | 13.0(46) |
| The Kenia service plate | 20.0(33) | 31.0(61) |
| Add up to | 33.0(119) | 65.0(228) |
Surprisingly, embodiment 2 shows, when the preparation that comprises zinc and bismuth and aluminium source (garlic press) combination, the corrosion protection of glassware is strengthened (comparing with the combination of zinc and bismuth).
In addition, realize the glassware corrosion protection strengthened, and do not observed usually any disadvantageous effect that the existence because of aluminium causes.Promptly do not observe iris and excessive turbidization of glass that the existence because of aluminium causes.
These effects all are beyond expectation.
In addition, said composition is not for all providing protection with the glassware of decorating and have a decoration.
Aluminium corrosion embodiment
In the present embodiment, use following detergent composition (shown in Table A L1a) as basic detergent formulations.Said preparation uses with tablet form.
Table A L1a
| Component | ％ |
| Tripoly phosphate sodium STPP | 45.0 |
| Sodium bicarbonate | 2.0 |
| Yellow soda ash | 18.5 |
| Sodium peroxoborate | 10.0 |
| TAED | 2.5 |
| Proteolytic enzyme | 1.5 |
| Amylase | 0.5 |
| Nonionogenic tenside | 3.5 |
| Polyoxyethylene glycol | 7.5 |
| Perfume compound+dyestuff | 0.3 |
| Assistant agent | Surplus |
Testing method
In aluminium embodiment, identical among used testing method and the glass embodiment.
The cleaning glass cup
Employed glass cylinder (have ornamental with do not have decoration) with in glass embodiment, use identical.The assessment of glass corrosion also with glass embodiment in identical mode carry out.
The aluminium dish
Two aluminium dishes are put in the dish-washing machine.Described plate comprises magnalium (aluminium of ALMg4:96% and 4% magnesium).Plate is of a size of 100mm * 50mm * 1.5mm, heavy 20g.
After 50～100 test washings, by the loss of weighting method assay determination weight.
Using following standard that aluminium is corroded assesses: aluminium variable color (DA) and flat light emission (SU).According to following table DA is given a mark.
| Assessment | Damage influence |
| 0 | Aluminium is damage not |
| 1 | A microlesion just/almost cannot see |
| 2 | The minor injury, the expert can see |
| 3 | Visible damage |
| 4 | Major injury, obviously as seen |
Use the determination techniques of " the Colour Guide Gloss " of basis to measure SU, this technology is used for the hand-held instrument from BYK Gardner GmbH company.Adopt D65/10 ° of setting and metering orifice is set in 11mm, carry out 10 assessments, carry out 10 assessments in the front of dish at the dish back side.Calculating is from the mean value of these 20 assess and determines.
Comparative example 1
In this comparative example, only use basic detergent formulations.
Test result is shown in Table A L2a (glass corrosion) and Table A L2b (mass loss).
Table A L2a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||||||
| 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 Klsch | 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 | ||
| On average | 1.57 | 1.07 | 2.06 | 2.93 | 1.93 | 2.75 | ||
| The glassware that has decoration | DS | IR | DS | IR | ||||
| Snoopy | 2.0 | - | 3.0 | - | ||||
| Teddy | 1.5 | - | 2.5 | - | ||||
| The Kenia service plate | 2.0 | 3.0 | 2.5 | 3.5 | ||||
| On average | 3.33 | - | 2.67 | - | ||||
| The aluminium dish | DA | DA | SU | |||||
| Dish | 1.0 | 1.5 | 4.1 | |||||
Table A L2b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 7 | 59 |
| Octime | 9 | 48 |
| Longchamp | 15 | 94 |
| RKG Klsch | 7 | 45.5 |
| RKG Bier | 6 | 72 |
| Nachtmann Longdrink | 15 | 124 |
| Arcoroc Elegance | 7 | 30 |
| Add up to | 66 | 472.5 |
| The glassware that has decoration | ||
| Snoopy | 25 | 502 |
| Teddy | 12 | 145 |
| The Kenia service plate | 20 | 230 |
| Add up to | 57 | 877 |
| The aluminium dish | ||
| Dish | 2138 | 4698 |
Comparative example 2
In this comparative example, only use basic detergent formulations.Sodium disilicate with 3.67g adds in the tablet formulation in addition.
Test result is shown in Table A L3a (glass corrosion) and Table A L3b (mass loss).
Table A L3a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||||||
| 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 Klsch | 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 | ||
| On average | 3.42 | 2.83 | 3.42 | 3.67 | 3.33 | 3.92 | ||
| The glassware that has decoration | DS | IR | DS | IR | ||||
| Snoopy | 3.0 | - | 3.5 | - | ||||
| Teddy | 3.0 | - | 3.5 | - | ||||
| The Kenia service plate | 1.5 | 4.0 | 2.0 | 4.0 | ||||
| On average | 2.5 | - | 3.0 | - | ||||
| The aluminium dish | DA | DA | SU | |||||
| Dish | 3.5 | 4.0 | 34.9 | |||||
Table A L3b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 29 | 52 |
| Octime | 15 | 22 |
| Longchamp | 76 | 109 |
| RKG Klsch | 15 | 27 |
| Nachtmann Longdrink | 46 | 90 |
| Arcoroc Elegance | 10 | 23 |
| Add up to | 192 | 323 |
| The glassware that has decoration | ||
| Snoopy | 130 | 256 |
| Teddy | 48 | 99 |
| The Kenia service plate | 45 | 76 |
| Add up to | 223 | 431 |
| The aluminium dish | ||
| Dish | 0.0 | 0.0 |
Comparative example 3
In this comparative example, only use basic detergent formulations.Zinc acetate with 0.67g adds in the tablet formulation in addition.
Test result is shown in Table A L4a (glass corrosion) and Table A L4b (mass loss).
Table A L4a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | |||||
| 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 Klsch | 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 | |
| On average | 0.67 | 1.00 | 0.58 | 1.08 | 1.33 | 0.58 | |
| The glassware that has decoration | DS | DS | |||||
| Snoopy | 1.0 | 2.0 | |||||
| Teddy | 1.0 | 1.5 | |||||
| The Kenia service plate | 1.0 | 2.5 | |||||
| On average | 1.00 | 2.00 | |||||
| The aluminium dish | DA | DA | SU | ||||
| Dish | 2.0 | 3.0 | 73.2 | ||||
Table A L4b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 15 | 16 |
| Octime | 2 | 0 |
| Longchamp | 7 | 17 |
| RKG Klsch | 0 | 0 |
| Nachtmann Longdrink | 1 | 8 |
| Arcoroc Elegance | 1 | 7 |
| Add up to | 26 | 48 |
| The glassware that has decoration | ||
| Snoopy | 14 | 32 |
| Teddy | 5 | 16 |
| The Kenia service plate | 17 | 41 |
| Add up to | 36 | 89 |
| The aluminium dish | ||
| Dish | 118 | 233 |
Comparative example 4
In this comparative example, only use basic detergent formulations.Bismuth citrate with 0.19g is added in the tablet formulation in addition.
Test result is shown in Table A L5a (glass corrosion) and Table A L5b (mass loss).
Table A L5a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | |||||
| 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 Klsch | 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 | |
| On average | 1.08 | 1.08 | 0.50 | 2.00 | 1.58 | 0.50 | |
| The glassware that has decoration | DS | DS | |||||
| Snoopy | 1.0 | 1.0 | |||||
| Teddy | 0.5 | 1.0 | |||||
| The Kenia service plate | 0.5 | 0.5 | |||||
| On average | 0.67 | 0.83 | |||||
| The aluminium dish | DA | DA | SU | ||||
| Dish | 3.0 | 4.0 | 28.0 | ||||
Table A L5b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 3 | 6 |
| Octime | 0.5 | 4.5 |
| Longchamp | 23 | 48 |
| RKG Klsch | 14 | 26.5 |
| Nachtmann Longdrink | 4 | 10 |
| Arcoroc Elegance | 5 | 5 |
| Add up to | 49.5 | 100 |
| The glassware that has decoration | ||
| Snoopy | 5 | 11 |
| Teddy | 0 | 7 |
| The Kenia service plate | 0 | 0 |
| Add up to | 5 | 18 |
| The aluminium dish | ||
| Dish | 104.5 | 217 |
Comparative example 1～4 shows, does not add the dissolving of protection aluminum, tarnishes and form iris on glassware.
Add sodium disilicate and can eliminate the dissolving of aluminum.But the color of aluminium changes, and its color transition becomes undesirable brownish black, and aluminum has also lost gloss.In addition, sodium disilicate produces negative effect to glassware: turbidization of glass, knife-line corrosion or even iris (because silicate rather than because aluminium) have taken place.In addition, the mass loss of glassware transparent and that have decoration increases, and decorates protection (being produced by dissolved aluminium) and has not also existed.
The adding of zinc acetate has reduced the mass loss (reach level when not having zinc 1/20) of aluminium dish.Iris and glass corrosion also improve.Yet, still not good enough to the performance of decorating protection.
The adding of bismuth citrate reduces the mass loss of aluminium dish, and the degree of minimizing is similar to the viewed degree of use zinc.Yet, the variable color aggravation of aluminium.The use of bismuth is done well aspect the glass protecting of decoration having, but performance is not good enough aspect the glass corrosion protection.
Embodiment 1
In the present embodiment, basic detergent formulations is used with 0.67g zinc acetate, 0.19g bismuth citrate and 3.8g sodium disilicate.
Test result is shown in Table A L6a (glass corrosion) and Table A L6b (mass loss).
Table A L6a-glass corrosion
| Glass cylinder | 50 circulations | 100 circulations | ||||||
| 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 Klsch | 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 | ||
| On average | 0.42 | 0.75 | 0.42 | 1.08 | 1.33 | 0.58 | ||
| The glassware that has decoration | DS | IR | DS | IR | ||||
| Snoopy | 0.0 | 0.5 | ||||||
| Teddy | 0.5 | 0.5 | ||||||
| The Kenia service plate | 0.0 | 0.0 | 1.0 | 0.0 | ||||
| On average | 0.17 | 0.67 | ||||||
| The aluminium dish | DA | DA | SU | |||||
| Dish | 0.5 | 1.0 | 124.83 | |||||
Table A L6b-mass loss
| Glass cylinder | 50 circulation mass losses (mg) | 100 circulation mass losses (mg) |
| Michelangelo | 2 | 4 |
| Octime | 0 | 0 |
| Longchamp | 1 | 0 |
| RKG Klsch | 5 | 5 |
| Nachtmann Longdrink | 3 | 2 |
| Arcoroc Elegance | 1 | 2 |
| Add up to | 12 | 13 |
| The glassware that has decoration | ||
| Snoopy | 2 | 2 |
| Teddy | 0 | 0 |
| The Kenia service plate | 0 | 0 |
| Add up to | 2 | 2 |
| The aluminium dish | ||
| Dish | 16 | 16 |
The result of embodiment 1 shows that the aluminium that exists for of zinc, bismuth and bisilicate combination provides excellent protection, thereby corrosion is reduced, and aluminium has kept its gloss.In addition, this combination minimizes the disadvantageous effect to glassware: all significantly weaken at simple glass vessel and the iris and the glass corrosion that have on the glassware of decoration.
Claims (20)
1. composition, said composition contains zinc and bismuth, be used for preventing glassware at the automatic tableware washing process owing to described glassware contacts the disadvantageous effect that is subjected to aluminium.
2. composition as claimed in claim 1, wherein in described composition the ratio of zinc and bismuth with the quality of these two kinds of metals count 1: 100～100: 1.
3. composition as claimed in claim 2, wherein the ratio of zinc and bismuth is 1: 10～10: 1 in mass in described composition, more preferably 1: 5～5: 1, most preferably is about 1: 1.
4. as claim 1,2 or 3 described compositions, wherein said zinc and/or bismuth are metallic forms.
5. composition as claimed in claim 4, wherein said metallic forms are the alloy of zinc and bismuth.
6. as claim 1,2 or 3 described compositions, wherein said zinc and/or bismuth exist as salt or compound.
7. composition as claimed in claim 6, wherein said salt/compound are nitrate, oxide compound, vitriol, phosphoric acid salt, halogenide, carbonate or carboxylate salt.
8. as each described composition of claim 1～7, wherein said composition comprises detergent formulations.
9. composition as claimed in claim 8, wherein said bismuth and zinc account for the 0.002 weight %～6 weight % of detergent formulations in the weight of these two kinds of metals.
10. composition as claimed in claim 9, wherein said bismuth and zinc account for the 0.01 weight %～3 weight % of detergent formulations, most preferably account for 0.02 weight %～1.3 weight % (for example 0.4 weight %).
11. as each described composition of claim 1～7, wherein said composition comprises rinse aid.
12. composition as claimed in claim 11, wherein said bismuth and zinc account for the 0.03 weight %～30 weight % of rinse aid in the weight of these two kinds of metals, more preferably account for 0.15 weight %～15 weight %, most preferably account for 0.3 weight %～7 weight %.
13. as each described composition of claim 1～7, wherein said composition comprises solubility ceramic/glass preparation.
14. the purposes of a composition, said composition contain zinc and bismuth, be used for preventing glassware at the automatic tableware washing process owing to described glassware contacts the disadvantageous effect that is subjected to aluminium.
15. purposes as claimed in claim 14, it is 1mg～1000mg that the described zinc to the dish-washing machine circulation and the amount of bismuth wherein are provided.
16. purposes as claimed in claim 15, it is 5mg～500mg that the described zinc to the dish-washing machine circulation and the amount of bismuth wherein are provided.
17. purposes as claimed in claim 16, the amount that the described zinc to the dish-washing machine circulation wherein is provided are that the amount of 5mg～100mg and described bismuth is 5mg～100mg.
18. a composition, said composition contains zinc, bismuth and aluminium, is used for preventing the glassware corrosion of automatic tableware washing machine.
19. a composition, said composition contains zinc, bismuth and silicate, is used for preventing the aluminium corrosion of automatic tableware washing machine.
20. a composition, said composition contains zinc, bismuth and silicate, is used for preventing the aluminium corrosion and the glassware corrosion of automatic tableware washing machine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0324295.5 | 2003-10-17 | ||
| GB0324295A GB0324295D0 (en) | 2003-10-17 | 2003-10-17 | Composition |
| GB0404469.9 | 2004-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1867657A true CN1867657A (en) | 2006-11-22 |
| CN100408662C CN100408662C (en) | 2008-08-06 |
Family
ID=29559443
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800306276A Expired - Fee Related CN1867521B (en) | 2003-10-17 | 2004-10-18 | Water-soluble glass composition |
| CNB2004800306261A Expired - Fee Related CN100408662C (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800306276A Expired - Fee Related CN1867521B (en) | 2003-10-17 | 2004-10-18 | Water-soluble glass composition |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN1867521B (en) |
| GB (2) | GB0324295D0 (en) |
| ZA (1) | ZA200602997B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408662C (en) * | 2003-10-17 | 2008-08-06 | 雷克特本克斯尔荷兰有限公司 | Composition for protection of glassware in dishwashers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067321B2 (en) | 2008-05-21 | 2011-11-29 | Icl Performance Products, Lp | Sodium-potassium hexametaphosphate and potassium metaphosphate with a low insolubles content |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1586067A (en) * | 1976-10-28 | 1981-03-18 | Procter & Gamble | Detergent composition |
| EP0070587B2 (en) * | 1981-07-17 | 1988-11-30 | THE PROCTER & GAMBLE COMPANY | Rinse aid composition |
| US5021366A (en) * | 1990-10-19 | 1991-06-04 | Corning Incorporated | Fluorine-free phosphate glasses |
| US5153151A (en) * | 1991-05-06 | 1992-10-06 | Corning Incorporated | High index fluorine-free phosphate glasses |
| EP0998548B1 (en) * | 1997-07-23 | 2004-09-29 | Unilever N.V. | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
| RU2167176C2 (en) * | 1997-10-07 | 2001-05-20 | Открытое акционерное общество Научно-производственное объединение "Искра" | Corrosion primer-transformer |
| DE10010209A1 (en) * | 2000-03-02 | 2001-09-13 | Reckitt Benckiser Nv | Use of ceramic dishwashing composition for protection of glassware from corrosion, involves using ceramic composition comprising at least one compound which releases active agent to protect glassware |
| CN1108279C (en) * | 2000-09-21 | 2003-05-14 | 华东理工大学 | A kind of phosphate glass |
| DE10104469A1 (en) * | 2001-02-01 | 2002-08-08 | Basf Ag | Copolymers to prevent glass corrosion |
| GB2372500B (en) * | 2001-02-22 | 2003-08-20 | Reckitt Benckiser Nv | Process for Inhibition of Corrosion of Glassware during Automatic Dishwashing |
| US7157391B2 (en) * | 2002-12-27 | 2007-01-02 | Hoya Corporation | Optical glass, preform for press molding and optical element |
| GB0324295D0 (en) * | 2003-10-17 | 2003-11-19 | Reckitt Benckiser Nv | Composition |
-
2003
- 2003-10-17 GB GB0324295A patent/GB0324295D0/en not_active Ceased
-
2004
- 2004-03-01 GB GB0404470A patent/GB2407097B/en not_active Expired - Fee Related
- 2004-10-18 CN CN2004800306276A patent/CN1867521B/en not_active Expired - Fee Related
- 2004-10-18 CN CNB2004800306261A patent/CN100408662C/en not_active Expired - Fee Related
-
2006
- 2006-04-12 ZA ZA200602997A patent/ZA200602997B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408662C (en) * | 2003-10-17 | 2008-08-06 | 雷克特本克斯尔荷兰有限公司 | Composition for protection of glassware in dishwashers |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200602997B (en) | 2007-09-26 |
| GB2407097A (en) | 2005-04-20 |
| CN1867521A (en) | 2006-11-22 |
| CN100408662C (en) | 2008-08-06 |
| GB0404470D0 (en) | 2004-03-31 |
| GB2407097B (en) | 2005-12-21 |
| GB0324295D0 (en) | 2003-11-19 |
| CN1867521B (en) | 2011-01-12 |
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