NO172354B - BLEACH MIXING - Google Patents
BLEACH MIXING Download PDFInfo
- Publication number
- NO172354B NO172354B NO895261A NO895261A NO172354B NO 172354 B NO172354 B NO 172354B NO 895261 A NO895261 A NO 895261A NO 895261 A NO895261 A NO 895261A NO 172354 B NO172354 B NO 172354B
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- Prior art keywords
- surfactant
- mixture
- solution
- hydrogen peroxide
- electrolyte
- Prior art date
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- 239000007844 bleaching agent Substances 0.000 title claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 71
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 12
- 150000003606 tin compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- -1 alkane sulfonate Chemical class 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 125000005011 alkyl ether group Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940079864 sodium stannate Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002978 peroxides Chemical group 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 3
- 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 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
Abstract
Oppløsninger av hydrogenperoksyd som er alkaliske, og som fortykkes med en kombinasjon av overflateaktivt middel og elektrolytt, kan stabiliseres med kolloidalt vannholdig tinn(IV)-oksyd.Solutions of hydrogen peroxide which are alkaline and which are thickened with a combination of surfactant and electrolyte can be stabilized with colloidal aqueous tin (IV) oxide.
Description
Denne oppfinnelse angår flytende blekemiddelblandinger som kan være fortykkede væsker egnet for salg og anvendelse som husholdnings-blekemiddel. Blandingene ifølge oppfinnelsen kan være hellbare væsker, skjønt de er mer viskøse enn vann, eller de kan være enda mer viskøse blandinger som ikke lett kan helles. Fortykning av et hellbart husholdnings-blekemiddel hjelper brukeren til å regulere fordeling av blandingen og forsinker avrenning fra overflater som det påføres på. This invention relates to liquid bleach mixtures which may be thickened liquids suitable for sale and use as household bleach. The mixtures according to the invention may be pourable liquids, although they are more viscous than water, or they may be even more viscous mixtures which cannot be easily poured. Thickening a pourable household bleach helps the user control the distribution of the mixture and delays runoff from surfaces to which it is applied.
Det er nødvendig at et husholdnings-blekemiddel er passende stabilt, slik at en hovedsakelig andel av blekemidlet holder seg under lagring mellom fremstilling og anvendelse. Forut for den foreliggende oppfinnelse er det i kommersielle flytende blekemiddelprodukter ofte blitt anvendt hypokloritt som blekemiddel. It is necessary for a household bleach to be suitably stable, so that a substantial proportion of the bleach remains during storage between manufacture and use. Prior to the present invention, commercial liquid bleach products often used hypochlorite as a bleaching agent.
Det er velkjent at hydrogenperoksyd er ustabilt dersom det ikke er stabiliseringsmidler tilstede. Disse motvirker dekomponering som katalyseres av overgangsmetal1ioner. Hydrogenperoksyd gir bedre blekevirkning hvis det anvendes under alkaliske betingelser. Imidlertid er stabilisering av hydrogenperoksyd under alkaliske betingelser vanskelig, og følgelig har kommersielle oppløsninger av hydrogenperoksyd vanligvis vært sure av hensyn til stabiliteten. It is well known that hydrogen peroxide is unstable if no stabilizers are present. These counteract decomposition catalyzed by transition metal ions. Hydrogen peroxide gives a better bleaching effect if used under alkaline conditions. However, stabilization of hydrogen peroxide under alkaline conditions is difficult, and consequently commercial solutions of hydrogen peroxide have usually been acidic for reasons of stability.
EP-B-9839 beskriver at stabiliseringen av hydrogenperoksyd under alkaliske betingelser kan skje under anvendelse av visse spesifiserte fosfonatforbindelser. Det inneholder også sammenligningsresultater som tester effektiviteten av forskjellige materialer og stabilisatorer under alkaliske betingelser. Disse sammenligningsresultater viser at mange materialer som er kjent for å stabilisere surt hydrogenperoksyd, har meget liten effekt under alkaliske betingelser. EP-B-9839 describes that the stabilization of hydrogen peroxide under alkaline conditions can take place using certain specified phosphonate compounds. It also contains comparative results testing the effectiveness of different materials and stabilizers under alkaline conditions. These comparative results show that many materials known to stabilize acidic hydrogen peroxide have very little effect under alkaline conditions.
Ett materiale som er blitt beskrevet som stabilisator for hydrogenperoksyd i sur oppløsning, er kolloidalt, vannholdig tinn(IV)-oksyd. US 3781409 og US 3607053 er eksempler på beskrivelser av anvendelse av natriumstannatet som stabiliseringsmiddel for sur hydrogenperoksydoppløsning. I disse US-patenter oppløses natriumstannatet i en alkalisk, men peroksyd-fri oppløsning, som så tilsettes som stabilisator til mye større volumdeler av sur hydrogenperoksyd-oppløsning. Natriumstannatet vil gjennomgå hydrolyse til kolloidalt vannholdig tinn(IV)-oksyd i oppløsningen. Den alkaliske oppløsning inneholder andre salter i tillegg til natriumstannat, men disse er fortynnet til et meget lavt elektrolyttnivå når de tilsettes til den sure hydrogen-peroksydoppløsning. One material that has been described as a stabilizer for hydrogen peroxide in acidic solution is colloidal hydrous tin(IV) oxide. US 3781409 and US 3607053 are examples of descriptions of the use of sodium stannate as a stabilizer for acidic hydrogen peroxide solution. In these US patents, the sodium stannate is dissolved in an alkaline but peroxide-free solution, which is then added as a stabilizer to much larger volumes of acidic hydrogen peroxide solution. The sodium stannate will undergo hydrolysis to colloidal aqueous tin(IV) oxide in the solution. The alkaline solution contains other salts in addition to sodium stannate, but these are diluted to a very low electrolyte level when added to the acidic hydrogen peroxide solution.
Hellbart flytende husholdningsblekemiddel fortykkes ofte ved at det innarbeides ett eller flere overflateaktive midler, som i nærvær av elektrolytt fortykker oppløsningen slik at den blir mer viskøs enn vann. Pourable liquid household bleach is often thickened by incorporating one or more surfactants, which in the presence of electrolyte thicken the solution so that it becomes more viscous than water.
Tilstedeværelsen av elektrolytt har tendens til å bevirke dekomponering av alkalisk hydrogenperoksydoppløsning. Vi har for eksempel funnet at en 4 vekt% oppløsning av hydrogenperoksyd, gjort alkalisk til pH 10 og inneholdende 0,25% etylendiamintetra-metylenfosfonsyre som stabilisator (som ikke er så effektiv som fosfonater i henhold til EP-B-9839), bevarer 95% av sitt hydrogenperoksyd etter to ukers lagring ved 37°C. I motsetning til dette ble 85% eller mindre av hydrogenperoksydet beholdt hvis oppløsningen også inneholdt 1 vekt% natriumklorid, mens bare ca. 50% av hydrogenperoksydet ble beholdt hvis oppløsningen inneholdt 10 vekt% natriumklorid. Lignende resultater ble observert ved anvendelse av natriumtripolyfosfat i stedet for natriumklorid som den tilsatte elektrolytt. Dobling av mengden av fosfonat-stabilisatoren hadde liten effekt på dekomponerings-hastigheten. The presence of electrolyte tends to cause decomposition of alkaline hydrogen peroxide solution. For example, we have found that a 4% by weight solution of hydrogen peroxide, made alkaline to pH 10 and containing 0.25% ethylenediaminetetramethylenephosphonic acid as a stabilizer (which is not as effective as phosphonates according to EP-B-9839), preserves 95 % of its hydrogen peroxide after two weeks of storage at 37°C. In contrast, 85% or less of the hydrogen peroxide was retained if the solution also contained 1% by weight sodium chloride, while only about 50% of the hydrogen peroxide was retained if the solution contained 10% by weight of sodium chloride. Similar results were observed using sodium tripolyphosphate instead of sodium chloride as the added electrolyte. Doubling the amount of the phosphonate stabilizer had little effect on the rate of decomposition.
Således vil et hvert forsøk på å fremstille et alkalisk, flytende husholdnings-blekemiddelprodukt fortykket ved overflateaktive midler, ved anvendelse av hydrogenperoksyd som blekemiddel, støte på det potensielle problem at fortykning av opp-løsningen ville fordre tilstedeværelse av en elektrolytt, men at denne elektrolytt ville tjene til å akselerere dekomponering av peroksydet. Thus, any attempt to produce an alkaline, liquid household bleach product thickened by surfactants, using hydrogen peroxide as a bleaching agent, will encounter the potential problem that thickening the solution would require the presence of an electrolyte, but that this electrolyte would serve to accelerate decomposition of the peroxide.
Et ytterligere potensielt problem oppstår på grunn av at en elektrolytt i seg selv har tendens til å frembringe flokkulering av kolloidale suspensjoner. Følgelig har tilstedeværelse av elektrolytt også potensiale til å frembringe en reduksjon av effektiviteten av ethvert stabiliseringsmiddel som er i form av en kolloidal suspensjon. A further potential problem arises because an electrolyte itself tends to cause flocculation of colloidal suspensions. Accordingly, the presence of electrolyte also has the potential to produce a reduction in the effectiveness of any stabilizer that is in the form of a colloidal suspension.
Det er overraskende at - som vi nå har funnet - kolloidalt vannholdig tinn(IV)-oksyd kan virke som et meget effektivt stabiliseringsmiddel for alkaliske hydrogenperoksydoppløsninger. Det er også overraskende at kolloidalt vannholdig tinn(IV)-oksyd vil tolerere innarbeidelse av overflateaktivt middel og elektrolytt i mengder som er tilstrekkelige til å bevirke fortykning. It is surprising that - as we have now found - colloidal aqueous tin(IV) oxide can act as a very effective stabilizer for alkaline hydrogen peroxide solutions. It is also surprising that colloidal aqueous tin(IV) oxide will tolerate the incorporation of surfactant and electrolyte in amounts sufficient to effect thickening.
Følgelig tilveiebringer foreliggende oppfinnelse en flytende blekemiddelblanding som er en alkalisk, vandig oppløsning inneholdende hydrogenperoksyd og også inneholdende kolloidalt vannholdig tinn(IV)-oksyd, se krav 1. Accordingly, the present invention provides a liquid bleach mixture which is an alkaline, aqueous solution containing hydrogen peroxide and also containing colloidal aqueous tin (IV) oxide, see claim 1.
Fortrinnsvis inneholder blandingen også et viskositetsøkende middel som er ett eller flere overflateaktive midler i nærvær av elektrolytt. Fortrinnsvis inneholder derfor en blanding ifølge oppfinnelsen også en annen elektrolytt enn overflateaktivt middel, sammen med minst ett overflateaktivt middel som, i nærvær av elektrolytt, tjener til å øke oppløsningens viskositet. Preferably, the mixture also contains a viscosity-increasing agent which is one or more surfactants in the presence of electrolyte. Preferably, therefore, a mixture according to the invention also contains an electrolyte other than surfactant, together with at least one surfactant which, in the presence of electrolyte, serves to increase the viscosity of the solution.
Det kolloidale, vannholdige tinn(IV)-oksyd som anvendes som stabiliseringsmiddel, dannes fortrinnsvis in situ i oppløsningen som hydrolyseproduktet av en løselig tinnforbindelse. En fremgangsmåte for fremstilling av en slik flytende blekemiddelblanding omfatter at man i blandingen innarbeider, suksessivt eller sammen, hydrogenperoksyd, tilstrekkelig alkalisk materiale til at oppløsningen får en alkalisk pH, og en tinnforbindelse som kan hydrolyseres til tinn(IV)-oksyd, slik at tinnforbindelsen hydrolyseres i oppløsningen til kolloidalt, vannholdig tinn(IV)-oksyd. Hydrolysen kan finne sted i en oppløsning som allerede er fortykket ved tilstedeværelse av overflateaktivt middel, skjønt peroksydet kanskje ikke er blitt tilsatt til oppløsningen ennå. Forskjellige tinnforbindelser som gjennomgår hydrolyse under dannelse av tinn(IV)-oksydet, kan tilsettes til oppløsningen. The colloidal, hydrous tin (IV) oxide used as stabilizer is preferably formed in situ in the solution as the hydrolysis product of a soluble tin compound. A method for the production of such a liquid bleach mixture comprises incorporating into the mixture, successively or together, hydrogen peroxide, sufficient alkaline material to give the solution an alkaline pH, and a tin compound which can be hydrolysed to tin (IV) oxide, so that the tin compound is hydrolyzed in the solution to colloidal, aqueous tin(IV) oxide. The hydrolysis may take place in a solution already thickened by the presence of surfactant, although the peroxide may not have been added to the solution yet. Various tin compounds which undergo hydrolysis to form the tin(IV) oxide can be added to the solution.
De foretrukkede er tinnsulfat og natriumstannat. Andre tinnforbindelser kan anvendes, innbefattende tinndiklorid og tinn-tetraklorid. The preferred ones are stannous sulfate and sodium stannate. Other stannous compounds may be used, including stannous dichloride and stannous tetrachloride.
Konsentrasjonene av tinnforbindelse som innarbeides i blandingen, vil ligge i området fra IO"<4> molar til IO"<2> molar, fortrinnsvis fra 3 x IO"<3> til 6 x IO"<3> molar. Mengde tinnforbindelse bør ikke være vesentlig større enn nødvendig, siden overskudd av den i seg selv kan bevirke peroksyd-dekomponering. En optimal konsentrasjon av tinnforbindelsen kan bestemmes ved fremstilling av testoppløsninger med forskjellige konsentrasjoner av tinnforbindelsen og analytisk bestemmelse av mengden peroksyd beholdt ved lagring. The concentrations of tin compound incorporated into the mixture will lie in the range from 10"<4> molar to 10"<2> molar, preferably from 3 x 10"<3> to 6 x 10"<3> molar. The amount of tin compound should not be significantly greater than necessary, since an excess of it in itself can cause peroxide decomposition. An optimal concentration of the tin compound can be determined by preparing test solutions with different concentrations of the tin compound and analytical determination of the amount of peroxide retained during storage.
Blandingene ifølge denne oppfinnelse skal ha en pH i området fra 8,5 til 9,3. En buffer kan innarbeides for fastsettelse av pH. The mixtures according to this invention must have a pH in the range from 8.5 to 9.3. A buffer can be incorporated to determine the pH.
Som allerede nevnt ovenfor, er det foretrukket å innarbeide minst ett overflateaktivt middel for økning av blandingens viskositet. Det er ønskelig at dette overflateaktive midlet eller overflateaktive midler har evne til å fortykke en opp-løsning i nærvær av en ganske lav elektrolyttkonsentrasjon. As already mentioned above, it is preferred to incorporate at least one surfactant to increase the viscosity of the mixture. It is desirable that this surface-active agent or surface-active agents have the ability to thicken a solution in the presence of a fairly low electrolyte concentration.
Dette kan gjøre det mulig at elektrolytten kan tilveiebringes av salter som er i blandingen for et annet formål, uten forsettlig tilsetning av et salt for det eneste formål å øke ionestyrken. Siden elektrolytter er kjent for å være skadelig for stabiliteten av hydrogenperoksyd, er det ønskelig å holde elektrolyttkonsentrasjonen lav. En ytterligere fordel med en lav elektrolyttkonsentrasjon er en redusert tendens til at blandingen etterlater striper på en overflate som renses med den. This may allow the electrolyte to be provided by salts which are in the mixture for another purpose, without the intentional addition of a salt for the sole purpose of increasing the ionic strength. Since electrolytes are known to be detrimental to the stability of hydrogen peroxide, it is desirable to keep the electrolyte concentration low. A further advantage of a low electrolyte concentration is a reduced tendency for the mixture to leave streaks on a surface cleaned with it.
Ett overflateaktivt middel som er egnet for bevirkning av fortykkelse, er alkyletersulfat med formelen: One surfactant suitable for effecting thickening is alkyl ether sulfate of the formula:
R(OC2H4)nOS03M R(OC 2 H 4 ) n OSO 3 M
hvor R er en alkylgruppe, fortrinnsvis rettkjedet alkyl, som inneholder 8-20 karbonatomer, n har en gjennomsnittsverdi i området fra 0,5 til 12, bedre fra 1 til 6, og M er et solubiliserende kation, fortrinnsvis alkalimetall så som natrium. where R is an alkyl group, preferably straight chain alkyl, containing 8-20 carbon atoms, n has an average value in the range from 0.5 to 12, preferably from 1 to 6, and M is a solubilizing cation, preferably an alkali metal such as sodium.
Et par overflateaktive midler som anvendes for bevirkning av fortykkelse, kan være en kombinasjon av et ikke-ionisk eller amfotært overflateaktivt middel sammen med et anionisk overflateaktivt middel. To spesifikke muligheter er kombinasjonene av: i) et overflateaktivt aminoksydmiddel, fortrinnsvis et trialkylaminoksyd med én langkjedet alkylgruppe på 8-20 A pair of surfactants used to effect thickening may be a combination of a nonionic or amphoteric surfactant together with an anionic surfactant. Two specific possibilities are the combinations of: i) an amine oxide surfactant, preferably a trialkylamine oxide with one long-chain alkyl group of 8-20
karbonatomer, og to alkylgrupper på 1-4 karbonatomer og carbon atoms, and two alkyl groups of 1-4 carbon atoms and
ii) et anionisk overflateaktivt middel som enten er primært alkoholsulfat med 8-20 karbonatomer i alkylgruppen, eller ii) an anionic surfactant which is either primary alcohol sulfate with 8-20 carbon atoms in the alkyl group, or
alkansulfonat som stammer fra alkan med 8-20 karbonatomer. alkane sulfonate derived from alkane with 8-20 carbon atoms.
Ytterligere overflateaktive midler kan også være til stede. Den totale mengde overflateaktivt middel (overflateaktive midler) som innarbeides, kan være en liten andel av blandingen; nærmere bestemt vil det fortykkende overflateaktive middel (midler) utgjøre fra 0,75 til 3% av blandingen. Additional surfactants may also be present. The total amount of surfactant(s) incorporated may be a small proportion of the mixture; more specifically, the thickening surfactant(s) will comprise from 0.75 to 3% of the mixture.
Når det anvendes primært alkoholsulfat, er vektforholdet mellom aminoksyd og alkoholsulfat fortrinnsvis i området fra 82:18 eller 80:20 til 65:35, bedre fra 80:20 til 70:30. When primarily alcohol sulfate is used, the weight ratio between amine oxide and alcohol sulfate is preferably in the range from 82:18 or 80:20 to 65:35, better from 80:20 to 70:30.
Alkansulfonat er foretrukket fremfor alkoholsulfat, fordi viskositeten er mindre følsom overfor forandringer i blandingen, hvorved det blir lettere å fremstille et sluttprodukt med repeterbar viskositet. Vektforholdet mellom aminoksyd og alkansulfonat er fortrinnsvis i området fra 80:20 til 50:50 eller 65:35, bedre fra 70:30 til 65:35. Alkanesulfonate is preferred over alcohol sulfate, because the viscosity is less sensitive to changes in the mixture, making it easier to produce a final product with repeatable viscosity. The weight ratio between amine oxide and alkanesulfonate is preferably in the range from 80:20 to 50:50 or 65:35, better from 70:30 to 65:35.
Elektrolyttkonsentrasjonen i en blanding ifølge denne oppfinnelse skal være slik at den totale mengde uorganiske salter, bortsett fra det overflateaktive middel, ikke er større enn 5 vekt%. Elektrolyttnivået kan være slik at det fåes en konsentrasjon av elektrolytt i området fra 0,05 til 0,30 molar, fortrinnsvis fra 0,1 til 0,2 molar. Det kan anvendes høyere konsentrasjoner, men dette er mindre foretrukket. The electrolyte concentration in a mixture according to this invention must be such that the total amount of inorganic salts, apart from the surfactant, is not greater than 5% by weight. The electrolyte level can be such that a concentration of electrolyte is obtained in the range from 0.05 to 0.30 molar, preferably from 0.1 to 0.2 molar. Higher concentrations can be used, but this is less preferred.
Det kreves at konsentrasjonen av hydrogenperoksyd i blandinger ifølge denne oppfinnelse, regnet som rent H202, ligger i området fra 1 til 15 vekt%, fortrinnsvis fra 2 til 10 vekt%. It is required that the concentration of hydrogen peroxide in mixtures according to this invention, calculated as pure H 2 O 2 , lies in the range from 1 to 15% by weight, preferably from 2 to 10% by weight.
En hensiktsmessig viskositet for en hellbar blanding med utseende av en tykk væske er en dynamisk viskositet i området fra 50 til 250 centipoise (0,05-0,25 Pa.sek), fortrinnsvis ca. 100 centipoise (0,1 Pa.sek). Mer viskøse væsker, for eksempel med viskositet i området fra 250 til 1000 centipoise eller mer, er også innenfor rammen av oppfinnelsen. A suitable viscosity for a pourable mixture with the appearance of a thick liquid is a dynamic viscosity in the range from 50 to 250 centipoise (0.05-0.25 Pa.sec), preferably approx. 100 centipoise (0.1 Pa.sec). More viscous liquids, for example with viscosities in the range of 250 to 1000 centipoise or more, are also within the scope of the invention.
Siden blandingene ifølge denne oppfinnelse vanligvis er vandige, vil de vanligvis ha en spesifikk vekt nær 1. Følgelig vil verdier for kinematiske viskositeter (i stoke) numerisk være omtrent de samme som verdier for dynamisk viskositet (i poise). Dynamiske viskositeter uttrykt i Pascal.sek vil være omtrent 1000 ganger kinetiske viskositeter uttrykt i m<2>.sek"<1>. Since the compositions of this invention are usually aqueous, they will usually have a specific gravity close to 1. Consequently, values for kinematic viscosities (in stokes) will numerically be approximately the same as values for dynamic viscosities (in poise). Dynamic viscosities expressed in Pascal.sec will be approximately 1000 times kinetic viscosities expressed in m<2>.sec"<1>.
Eksempel 1 Example 1
Det ble fremstilt preparater som inneholdt bestanddelene Preparations containing the components were produced
oppført i tabell 1 nedenfor. Blandingene ble lagret i plast- listed in Table 1 below. The mixtures were stored in plastic
flasker ved 37°C. Med mellomrom ble porsjoner fjernet og titrert med kaliumpermanganat for bestemmelse av nivået av gjenværende hydrogenperoksyd. Resultatene er medtatt i tabell 1. bottles at 37°C. At intervals, aliquots were removed and titrated with potassium permanganate to determine the level of residual hydrogen peroxide. The results are included in table 1.
Disse preparaters viskositet ble målt under anvendelse av The viscosity of these preparations was measured using
et kapillar-viskosimeter av typen Ubbelohde og funnet å være ca. 100 cS. a capillary viscometer of the Ubbelohde type and found to be approx. 100 cS.
Stabilisatoren i henhold til EP 9839 var The stabilizer according to EP 9839 was
dietylentriaminpenta(metylenfosfonsyre). diethylenetriaminepenta(methylenephosphonic acid).
Eksempel 2 Example 2
Fremgangsmåten ifølge eksempel 1 ble gjentatt under anvendelse av preparater med de samme mengder hydrogenperoksyd, overflateaktivt middel, parfyme og fargestoff. Forskjellige tinnforbindelser ble anvendt ved en konsentrasjon på 6 x IO"<3 >molar, men med og uten 3,0% boraksdekahydrat. Glassflasker ble anvendt, hvilket er noe skadelig for stabiliteten. I hvert tilfelle var pH 9,6 i begynnelsen. Andeler av hydrogenperoksyd som var tilbake etter 28 dager, var: The procedure according to example 1 was repeated using preparations with the same amounts of hydrogen peroxide, surfactant, perfume and dye. Various tin compounds were used at a concentration of 6 x 10"<3 >molar, but with and without 3.0% borax decahydrate. Glass bottles were used, which is somewhat detrimental to stability. In each case the initial pH was 9.6. Proportions of hydrogen peroxide that remained after 28 days was:
Eksempel 3 Example 3
Fremgangsmåten ifølge eksempel 1 ble gjentatt under anvendelse av et annet overflateaktivt middel og med tinn(II)-klorid som tinnsalt. Det anvendte overflateaktive middel var et rettkjedet alkyletersulfat med den generelle formel: hvor alkylgruppen R var rettkjedete C12- og C13- alkylgrupper, og n hadde en gjennomsnittlig verdi på 3. Et sammenligningsforsøk erstattet tinn(II)-kloridet med den samme fosfonat-stabilisator ifølge EP 9839 som anvendt i eksempel 1. Sammensetningene og resultatene er oppført i følgende tabell. Viskositetene ble bestemt under anvendelse av et roto-viskosimeter av typen Haake og var ca. 100 cP ved en skjærhastighet på 21 sek"<1>. The procedure according to example 1 was repeated using a different surface-active agent and with stannous chloride as stannous salt. The surfactant used was a straight-chain alkyl ether sulfate with the general formula: where the alkyl group R was straight-chain C12 and C13 alkyl groups, and n had an average value of 3. A comparative experiment replaced the stannous chloride with the same phosphonate stabilizer according to EP 9839 as used in Example 1. The compositions and results are listed in the following table. The viscosities were determined using a roto-viscometer of the Haake type and were approx. 100 cP at a shear speed of 21 sec"<1>.
Eksempel 4 Example 4
En alkalisk oppløsning av hydrogenperoksyd ble fremstilt, som inneholdt 4 vekt% hydrogenperoksyd (regnet som vannfritt) og natriumhydroksyd for oppnåelse av en pH på 10, og en 5,7 x 10"<3 >molar mengde av tinn(IV)-klorid som ble hydrolysert til kolloidalt vannholdig tinn(IV)-oksyd. An alkaline solution of hydrogen peroxide was prepared, containing 4% by weight of hydrogen peroxide (calculated as anhydrous) and sodium hydroxide to achieve a pH of 10, and a 5.7 x 10"<3 >molar amount of stannous chloride which was hydrolyzed to colloidal aqueous tin(IV) oxide.
Blandingen ble lagret ved 40°C, og mengden gjenværende hydrogenperoksyd ble bestemt analytisk ved intervaller. Det ble funnet at 75% av hydrogenperoksydet var igjen etter 3 uker. The mixture was stored at 40°C, and the amount of residual hydrogen peroxide was determined analytically at intervals. It was found that 75% of the hydrogen peroxide remained after 3 weeks.
Skjønt denne test ble utført uten overflateaktivt middel eller mye elektrolytt til stede, bekrefter den effektiviteten av kolloidalt tinn(IV)-oksyd som stabilisator i alkalisk oppløsning. Although this test was performed without surfactant or much electrolyte present, it confirms the effectiveness of colloidal tin(IV) oxide as a stabilizer in alkaline solution.
Eksempel 5 Example 5
Alkaliske oppløsninger av hydrogenperoksyd ble fremstilt som inneholdt overflateaktivt middel, natriumklorid og tinn(IV)-klorid, som ble hydrolysert til kolloidalt vannholdig tinn(IV)-oksyd. To kombinasjoner av overflateaktivt middel ble anvendt. Alkaline solutions of hydrogen peroxide were prepared containing surfactant, sodium chloride and tin(IV) chloride, which were hydrolysed to colloidal aqueous tin(IV) oxide. Two combinations of surfactant were used.
Mengdene av overflateaktivt middel og natriumklorid var slik at man fikk viskositeter som var langt større enn det som er foretrukket for en hellbar blekemiddelprodukt-type. Mindre mengder kunne anvendes for oppnåelse av et blekemiddelprodukt av typen "tykk væske". The amounts of surfactant and sodium chloride were such that viscosities were obtained that were far greater than that preferred for a pourable type of bleach product. Smaller amounts could be used to obtain a "thick liquid" type bleach product.
I hvert tilfelle var konsentrasjonen av hydrogenperoksyd, regnet som vannfri, 4 vekt%. Oppløsningene ble gjort alkalisk til pH 10 med natriumhydroksyd. In each case, the concentration of hydrogen peroxide, calculated as anhydrous, was 4% by weight. The solutions were made alkaline to pH 10 with sodium hydroxide.
Tinn(IV)-klorid ble anvendt i en konsentrasjon 2,3 x 10"<3 >molar. Tin (IV) chloride was used at a concentration of 2.3 x 10"<3 >molar.
Ett overflateaktivt-middel-system bestod av 4,5 vekt% C12-C14-alkyldimetylaminoksyd og 4,5 vekt% natriumlaurylsulfat. Dette ble anvendt med en natriumkloridkonsentrasjon på 9 vekt%. One surfactant system consisted of 4.5 wt% C12-C14 alkyldimethylamine oxide and 4.5 wt% sodium lauryl sulfate. This was used with a sodium chloride concentration of 9% by weight.
Det annet overflateaktivt-middel-system bestod av 5 vekt% av C^-Cjg-sek.-alkohol etoksylert med gjennomsnittlig 3 etylen-oksydrester, og 5 vekt% natriumlaurylsulfat. Denne kombinasjon ble anvendt med 3,37 vekt% natriumklorid. The second surfactant system consisted of 5% by weight of C₁-C₂-sec alcohol ethoxylated with an average of 3 ethylene oxide residues, and 5% by weight of sodium lauryl sulfate. This combination was used with 3.37% by weight of sodium chloride.
Oppløsningene ble lagret ved 40°C, og mengden gjenværende hydrogenperoksyd ble bestemt ved intervaller. Det ble funnet at mengdene av hydrogenperoksyd som var igjen, var mellom 80 og 85% med hver av overflateaktivt-middel-kombinasjonene. The solutions were stored at 40°C, and the amount of residual hydrogen peroxide was determined at intervals. The amounts of hydrogen peroxide remaining were found to be between 80 and 85% with each of the surfactant combinations.
Eksempel 6 Example 6
En basis-oppløsning ble fremstilt som inneholdende talg-dimetylaminoksyd, natriumalkansulfonat og boraks. Denne ble anvendt til dannelse av oppløsninger som inneholdt hydrogenperoksyd og kolloidalt tinn(IV)-oksyd, men det ble anvendt to fremgangsmåter. A base solution was prepared containing tallow dimethylamine oxide, sodium alkanesulfonate and borax. This was used to form solutions containing hydrogen peroxide and colloidal tin (IV) oxide, but two methods were used.
Ved én fremgangsmåte ble tinn(II)-klorid-dihydrat tilsatt til basisoppløsningen og omrørt inntil det var fullstendig oppløst eller dispergert, hvoretter hydrogenperoksydoppløsning ble tilsatt. Oppløsnings-pH på dette trinn var 6,5. Den ble justert til pH 9,9 ved tilsetning av 20 vekt/volum% natrium-hydroksydoppløsning og en del destillert vann. In one method, stannous chloride dihydrate was added to the base solution and stirred until completely dissolved or dispersed, after which hydrogen peroxide solution was added. The solution pH at this stage was 6.5. It was adjusted to pH 9.9 by the addition of 20% w/v sodium hydroxide solution and a portion of distilled water.
De anvendte mengder var slik at blandingen inneholdt: The amounts used were such that the mixture contained:
Ved den alternative fremgangsmåte ble det fremstilt en suspensjon av tinn(IV)-oksyd ved oppløsning av 5 g tinn(II)-klorid-dihydrat i ca. 115 g destillert vann, og deretter tilsetning av natriumhydroksydoppløsning under oppnåelse av en pH på 9,7. Den resulterende suspensjon av tinn(IV)-oksyd ble lagret over natten. In the alternative method, a suspension of tin (IV) oxide was prepared by dissolving 5 g of tin (II) chloride dihydrate in approx. 115 g of distilled water, and then addition of sodium hydroxide solution, achieving a pH of 9.7. The resulting tin(IV) oxide suspension was stored overnight.
Hydrogenperoksyd ble tilsatt til basis-oppløsningen, fulgt av natriumhydroksydoppløsning og en del destillert vann under oppnåelse av en pH på 9,9. En liten suspensjonsmengde ble så tilsatt. Dette ble beregnet å være den suspensjonsmengde som ble dannet av 0,14 g SnCl2.2H20. Andre mengder var som ved den første fremgangsmåte. Hydrogen peroxide was added to the base solution, followed by sodium hydroxide solution and a portion of distilled water, achieving a pH of 9.9. A small amount of suspension was then added. This was calculated to be the amount of suspension formed by 0.14 g of SnCl2.2H20. Other amounts were as in the first procedure.
Oppløsningene ble begge lagret ved 37"C (for akselerert aldring) og konsentrasjonen av gjenværende hydrogenperoksyd ble bestemt ved analyse etter 48 og 120 timer. Resultatene var som følger: The solutions were both stored at 37°C (for accelerated aging) and the concentration of residual hydrogen peroxide was determined by analysis after 48 and 120 hours. The results were as follows:
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888830296A GB8830296D0 (en) | 1988-12-28 | 1988-12-28 | Bleaching composition |
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| NO895261L NO895261L (en) | 1990-06-29 |
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| NO172354C NO172354C (en) | 1993-07-07 |
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| NO895261A NO172354C (en) | 1988-12-28 | 1989-12-27 | BLEACH MIXING |
| NO895260A NO173885C (en) | 1988-12-28 | 1989-12-27 | Bleach Mixture |
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| GB8830296D0 (en) * | 1988-12-28 | 1989-02-22 | Unilever Plc | Bleaching composition |
| DE4123142A1 (en) * | 1991-07-12 | 1993-01-14 | Henkel Kgaa | FLUESSIGWASCHMITTEL |
| US5217710A (en) * | 1992-03-05 | 1993-06-08 | Chesebrough-Pond's Usa Co. | Stabilized peroxide gels containing fluoride |
| GB9319943D0 (en) * | 1993-09-28 | 1993-11-17 | Solvay Interox Ltd | Thickened compositions |
| GB2286603B (en) * | 1994-02-14 | 1998-03-25 | Jeyes Group Plc | Bleach compositions |
| DE4413433C2 (en) * | 1994-04-18 | 1999-09-16 | Henkel Kgaa | Aqueous bleach |
| US5492540A (en) * | 1994-06-13 | 1996-02-20 | S. C. Johnson & Son, Inc. | Soft surface cleaning composition and method with hydrogen peroxide |
| DK0769047T3 (en) * | 1994-07-01 | 1999-09-27 | Warwick Int Group | Bleaching Compositions |
| US5736497A (en) * | 1995-05-05 | 1998-04-07 | Degussa Corporation | Phosphorus free stabilized alkaline peroxygen solutions |
| DE19623571C2 (en) * | 1996-06-13 | 2000-06-08 | Cognis Deutschland Gmbh | Thickener for aqueous hydrogen peroxide solutions |
| BR9704210A (en) * | 1997-07-31 | 1999-02-02 | Unilever Nv | Detergent composition and dish washing process |
| GB9812457D0 (en) * | 1998-06-10 | 1998-08-05 | Secr Defence | Surface coatings |
| AU741580B2 (en) * | 1998-06-23 | 2001-12-06 | Saban Ventures Pty Limited | Improved disinfection |
| ATE293675T1 (en) * | 1998-10-22 | 2005-05-15 | Colgate Palmolive Co | THICKENED LIQUID HYDROGEN PEROXIDE BLEACH COMPOSITION |
| GB2349892A (en) * | 1999-05-13 | 2000-11-15 | Warwick Internat Group Ltd | Metal cleaning |
| GB2397823A (en) * | 2003-01-31 | 2004-08-04 | Reckitt Benckiser Nv | Aqueous cleaning compositions |
| GB2401875A (en) * | 2003-05-22 | 2004-11-24 | Reckitt Benckiser Nv | Aqueous cleaning compositions |
| ITMI20031543A1 (en) * | 2003-07-28 | 2005-01-29 | De Nora Elettrodi Spa | ELECTRODE FOR ELECTROCHEMICAL PROCESSES AND METHOD FOR ITS ACHIEVEMENT |
| US7169237B2 (en) | 2004-04-08 | 2007-01-30 | Arkema Inc. | Stabilization of alkaline hydrogen peroxide |
| US7431775B2 (en) | 2004-04-08 | 2008-10-07 | Arkema Inc. | Liquid detergent formulation with hydrogen peroxide |
| US7045493B2 (en) | 2004-07-09 | 2006-05-16 | Arkema Inc. | Stabilized thickened hydrogen peroxide containing compositions |
| DE102005000955B4 (en) * | 2005-01-07 | 2007-08-30 | Henkel Kgaa | Liquid bleach composition |
| CN105925398B (en) * | 2016-05-17 | 2018-11-23 | 河南工程学院 | A kind of degerming liquid detergent composition and preparation method thereof |
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| DE1271885B (en) * | 1964-01-04 | 1968-07-04 | Henkel & Cie Gmbh | Liquid, storage-stable detergents, bleaching agents and oxidizing agents |
| US3701825A (en) * | 1970-10-23 | 1972-10-31 | Fmc Corp | Stabilization of hydrogen peroxide with ethylenediamine tetra (methylenephosphonic acid) |
| FR2140822A5 (en) * | 1971-06-09 | 1973-01-19 | Air Liquide | Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers |
| US4304762A (en) * | 1978-09-27 | 1981-12-08 | Lever Brothers Company | Stabilization of hydrogen peroxide |
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| DE3168426D1 (en) * | 1980-04-01 | 1985-03-07 | Interox Chemicals Ltd | Liquid detergent compositions, their manufacture and their use in washing processes |
| JPS56151798A (en) * | 1980-04-01 | 1981-11-24 | Interox Chemicals Ltd | Liquid detergent composition |
| JPS5838800A (en) * | 1981-09-01 | 1983-03-07 | 三菱瓦斯化学株式会社 | Liquid detergent |
| DE3205318A1 (en) * | 1982-02-15 | 1983-08-18 | Henkel KGaA, 4000 Düsseldorf | DISINFECTANT CONCENTRATE |
| CA1205275A (en) * | 1982-06-14 | 1986-06-03 | Kenneth J. Radimer | Stabilization of high purity hydrogen peroxide |
| JPS593006A (en) * | 1982-06-14 | 1984-01-09 | エフ・エム・シ−・コ−ポレ−シヨン | Method of stabilizing high-purity hydrogen peroxide |
| FR2552124B1 (en) * | 1983-09-20 | 1986-09-12 | Ugine Kuhlmann | NOVEL FLUID FORMULATIONS FOR STORAGE-STABLE TEXTILE BLEACH BATHS AND PROCESS FOR OBTAINING SAME |
| JP2783999B2 (en) * | 1985-06-12 | 1998-08-06 | 花王株式会社 | Bleach composition |
| GB8830296D0 (en) * | 1988-12-28 | 1989-02-22 | Unilever Plc | Bleaching composition |
-
1988
- 1988-12-28 GB GB888830296A patent/GB8830296D0/en active Pending
-
1989
- 1989-12-21 ZA ZA899842A patent/ZA899842B/en unknown
- 1989-12-21 ZA ZA899843A patent/ZA899843B/en unknown
- 1989-12-22 AU AU47271/89A patent/AU623961B2/en not_active Ceased
- 1989-12-22 AU AU47272/89A patent/AU624209B2/en not_active Ceased
- 1989-12-22 CA CA002006530A patent/CA2006530C/en not_active Expired - Fee Related
- 1989-12-22 CA CA002006531A patent/CA2006531C/en not_active Expired - Fee Related
- 1989-12-27 IN IN355/BOM/89A patent/IN170708B/en unknown
- 1989-12-27 EP EP89313625A patent/EP0376706B1/en not_active Expired - Lifetime
- 1989-12-27 EP EP89313623A patent/EP0376704B1/en not_active Expired - Lifetime
- 1989-12-27 ES ES89313623T patent/ES2067558T3/en not_active Expired - Lifetime
- 1989-12-27 ES ES89313625T patent/ES2067559T3/en not_active Expired - Lifetime
- 1989-12-27 IN IN354/BOM/89A patent/IN171127B/en unknown
- 1989-12-27 NO NO895261A patent/NO172354C/en not_active IP Right Cessation
- 1989-12-27 DE DE68921182T patent/DE68921182T2/en not_active Expired - Fee Related
- 1989-12-27 DE DE68921181T patent/DE68921181T2/en not_active Expired - Fee Related
- 1989-12-27 NO NO895260A patent/NO173885C/en not_active IP Right Cessation
- 1989-12-28 JP JP1345128A patent/JP2562064B2/en not_active Expired - Fee Related
- 1989-12-28 JP JP1345129A patent/JPH0735520B2/en not_active Expired - Lifetime
- 1989-12-28 BR BR898906844A patent/BR8906844A/en not_active IP Right Cessation
- 1989-12-28 BR BR898906843A patent/BR8906843A/en not_active IP Right Cessation
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| MM1K | Lapsed by not paying the annual fees |
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