WO2013178289A1 - Stabilization of phthalimido percarboxylic with lithium salts - Google Patents
Stabilization of phthalimido percarboxylic with lithium salts Download PDFInfo
- Publication number
- WO2013178289A1 WO2013178289A1 PCT/EP2012/060448 EP2012060448W WO2013178289A1 WO 2013178289 A1 WO2013178289 A1 WO 2013178289A1 EP 2012060448 W EP2012060448 W EP 2012060448W WO 2013178289 A1 WO2013178289 A1 WO 2013178289A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- phthalimido
- acid
- mixture
- mixture according
- Prior art date
Links
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 34
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 34
- 125000005544 phthalimido group Chemical group 0.000 title claims description 21
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 68
- -1 phthalimido percarboxylic acid Chemical compound 0.000 claims abstract description 42
- 239000003599 detergent Substances 0.000 claims abstract description 24
- 239000007844 bleaching agent Substances 0.000 claims abstract description 11
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 150000007513 acids Chemical class 0.000 claims description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 15
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 11
- FSBGUSGSQKUNCC-UHFFFAOYSA-N 2-(1,3-dioxoisoindol-2-yl)hexaneperoxoic acid Chemical compound C1=CC=C2C(=O)N(C(CCCC)C(=O)OO)C(=O)C2=C1 FSBGUSGSQKUNCC-UHFFFAOYSA-N 0.000 claims description 10
- 150000004645 aluminates Chemical class 0.000 claims description 6
- SUPUVLWGKPVHBQ-UHFFFAOYSA-M lithium sulfite Chemical compound [Li+].OS([O-])=O SUPUVLWGKPVHBQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 3
- 125000005024 alkenyl aryl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- HPCCWDVOHHFCKM-UHFFFAOYSA-M lithium;hydrogen sulfate Chemical compound [Li+].OS([O-])(=O)=O HPCCWDVOHHFCKM-UHFFFAOYSA-M 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910007549 Li2SiF6 Inorganic materials 0.000 claims 1
- 229910012223 LiPFe Inorganic materials 0.000 claims 1
- 150000001450 anions Chemical class 0.000 description 5
- 239000012038 nucleophile Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 150000004967 organic peroxy acids Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- WTQMRYVXRLESSC-UHFFFAOYSA-N 2-(6-hydroxyhexan-3-yl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(CCCO)CC)C(=O)C2=C1 WTQMRYVXRLESSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 101150070177 ubi4 gene Proteins 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- 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
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
-
- 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
Definitions
- the present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
- organic peracids have encountered increasing interest in the industrial field, among others due to their excellent properties as bleaching agents in detergent formulations. Therefore, a large number of publications are concerned with organic peracid compounds endowed with the required property of sufficient bleaching activity, said characteristic being essential for an industrial application and a widespread use of such compounds.
- organic straight-chain or cyclic mono- or dipercarboxylic acids are known and used, e.g. in detergent compositions.
- boric acid As boric acid has become a chemical of high concern, it is to be expected that boric acid will be banned from use in domestic applications in the near future.
- the present invention satisfies this need by providing a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
- a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
- phthalimido percarboxylic acids can be stabilized by lithium salts. This is rather surprising since it was suggested by the prior art that phthalimido percarboxylic acids if not stabilized degrade following a radical reaction pathway.
- phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
- PAP phthalimido percaproic acid
- nucleophilic reaction sites at PAP and/or by catching nucleophiles with electrophiles other than PAP.
- the present invention is directed to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
- the at least one lithium salt may be either organic or inorganic.
- the at least one lithium salt may be hydrous or anhydrous.
- the present invention also relates to the mixture described above, characterized in that it comprises at least one inorganic lithium salt.
- the present invention further relates to the mixture described above, characterized in that it comprises at least one organic lithium salt.
- the anion of the at least one lithium salt is rather non-nucleophilic. If the anion in question is too nuc!eophilic, it is assumed to compete against the lithium cation for interaction with the phthalimido percarboxylic acid.
- Suitable non-nucleophilic anions for use according to the present invention are hexafluorosilicate (SiF 6 2" ), sulfite (S0 3 2” ), hydrogensulfite (HS0 3 ⁇ ), organosulfite (RS0 3 ⁇ ), sulfate (S0 4 2” ), hydrogensulfate (HS0 4 " ), organosulfate (RS0 4 " ), phosphate (PO4 3 ), hydrogenphosphate (HPO4 2” ).
- R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof, wherein the sulfate anion represents the most preferred anion.
- the present invention also relates to the mixture described above, characterized in that it comprises at least one lithium salt is selected from the group consisting of lithium hexafluorosilicate (L ⁇ SiFe), lithium sulfite (U2SO3), lithium hydrogensulfite (L1HSO3), lithium organosulfite (Li 2 RS0 3 ), lithium sulfate (Li 2 S0 4 ), lithium hydrogensulfate (LJHSO4), lithium organosulfate (LiRS0 4 ), lithium phosphate (Li 3 P0 4 ), lithium hydrogenphosphate ⁇ U2HPO4), lithium dihydrogenphosphate
- LiPF 6 lithium hexachloro aluminate
- Li 3 AICI 6 lithium hexabromo aluminate
- Li 3 AIBr 6 lithium salt of an organic acid
- R is selected from the group of Ci to C 30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof.
- the present invention further relates to the mixture as described above, characterized in that it comprises lithium sulfate. Also, there is no restriction as concerns the chemical nature of the at least one phthalimido percarboxylic acid. Suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the phthalimido
- n is an integer of from 1 to 5:
- phthalimido percaproic acid phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP)
- the present invention also relates to the mixture described above, characterized in that it comprises at least one phthalimido percarboxylic acid selected from the phthalimido percarboxylic acids of the general formula (I) above, where n is an integer of from 1 to 5.
- the present invention further relates to the mixture described above, characterized in that it comprises phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP).
- Phthalimido percarboxylic acids and especially phthalimido peroxycarproic acid may be prepared as described in EP 0 325 288 A1 and EP 0 349 940 B1 , respectively.
- a substrate selected from phthalimido carboxylic acids and anhydrides thereof having a structure corresponding to the desired percarboxylic acid, e.g. of the general formula (I) may be reacted with concentrated H2O2 in a reaction medium selected from concentrated H 2 S0 4 and CH3SO3H or in an alkaline medium, and the
- percarboxylic acid is then separated from the reaction mixture by conventional and known techniques.
- the content of lithium salt in the mixture should range between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
- the present invention also relates to the mixture described above, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
- the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
- the present invention also relates to the mixture described above, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1:1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
- An especially expedient mixture for use as a bleaching agent comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
- the present invention also relates to the mixture described above, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
- phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
- lithium sulfate based on the total weight of the mixture.
- the mixture comprising the at least one phthalimido percarboxylic acid and the at least one lithium salt according to the present invention may be manufactured in the form of an aqueous solution, gel, emulsion, paste, dispersion, powder, flake, granules, scales, pearls, tablets, solid block form, extrudates and other forms known in the art, but preferably represents a powder or a flake.
- the present invention also relates to the mixture described above, characterized in that the mixture is in the form of a powder or a flake.
- the mixture according to the present invention is particularly suitable as effective bleaching agent in detergent formulations.
- the present invention is also directed to the use of a mixture described above as a bleaching agent.
- the present invention is further directed to a detergent composition comprising a mixture described above.
- the detergent composition may contain any additive or active ingredient commonly used in corresponding washing, cleansing and/or disinfecting agents like builders, surfactants, soaps, zeolites, hydrotropic agents, corrosion inhibitors, enzymes, optical brighteners, stabilizers, abrasives, perfumes, coloring agents.
- inventive mixture may be incorporated into the detergent composition either as such or in combination with further additives, for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc. in the forms mentioned above for the mixture.
- further additives for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc.
- the detergent composition is substantially free of boric acid, i.e. comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
- the present invention also relates to the detergent composition described before, characterized in that it comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
- the detergent composition may be used as a laundry detergent, preferably as a textile detergent, and is not only suitable for generally washing laundry, but as well for disinfecting.
- the detergent according to the present application may be used as cleanser and/or disinfectant for cleansing and disinfecting various kinds of hard surfaces like, for example, in the medicinal or institutional field, in the food preparing, processing and/or selling industry, in agriculture, in hotel business, catering trade and/or in public buildings and/or institutions. It may as well be useful in further applications in which a disinfected surface is required or desired and which are not explicitly mentioned herein.
- the surfaces supposed to become disinfected may be made of common materials mentioned in the state of the art like, for example, metal, glass, ceramic, plastic, (coated) wood.
- the present invention relates to the use of at least one lithium salt for stabilizing a phthalimido percarboxy!ic acid in a detergent composition.
- a mixture for use as a bleaching agent comprising 86 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and 14 % by weight of a stabilizing agent (example 1a: boric acid (comparative); example 1 b: sodium sulfate (comparative); example 1c: lithium sulfate) was tested for its long-term stability. Therefore, the amount of chemically active PAP in the respective mixture was determined after storage by 40 °C at 1 , 3, 7, 14, 21 , 28, 49, 84, 119, 161 and 2 0 days, respectively.
- a mixture comprising lithium sulfate shows a significantly higher long-term stability of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) than a mixture comprising sodium sulfate (example 1b).
- phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
- a lithium salt according to the present invention example 1c
- boric acid conventionally used example 1a
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
Description
Stabilization of phthalimido percarboxylic acids with lithium salts
FIELD OF THE INVENTION
The present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
BACKGROUND OF THE INVENTION
In the past, organic peracids have encountered increasing interest in the industrial field, among others due to their excellent properties as bleaching agents in detergent formulations. Therefore, a large number of publications are concerned with organic peracid compounds endowed with the required property of sufficient bleaching activity, said characteristic being essential for an industrial application and a widespread use of such compounds. Thus, many organic straight-chain or cyclic mono- or dipercarboxylic acids are known and used, e.g. in detergent compositions.
A problem with the widespread use of organic peracids arises from their low thermal stability, which makes it necessary to physically or chemically stabilize these compounds. The organic peracids known so far show a significant decrease of active oxygen, even under conventional storage conditions. This is also the case with imido percarboxylic acids as described already in J. Chem. Soc. 1962, 3821 and Chem. Ind. 1961 , 469. Among the imido percarboxylic acids, phthalimido percarboxylic acids have gained a widespread use in industry, especially as bleaching agents in detergent compositions. However, addition of boric acid to phthalimido percarboxylic acids is considered necessary to guarantee a sufficient long-term stability.
As boric acid has become a chemical of high concern, it is to be expected that boric acid will be banned from use in domestic applications in the near future.
Consequently, there is a need for alternative ways of stabilizing phthalimido percarboxylic acids in detergent compositions without making use of boric acid.
SUMMARY OF THE INVENTION
The present invention satisfies this need by providing a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt. With the present invention, it is possible to stabilize phthalimido percarboxylic acids so as to minimize a decrease of oxygen under conventional storage conditions, but to avoid the use of boric acid. Thus, detergent compositions may be obtained showing sufficient bleaching activity over time.
DETAILED DESCRIPTION OF THE INVENTION
After extensive studies, the inventors have found that phthalimido percarboxylic acids can be stabilized by lithium salts. This is rather surprising since it was suggested by the prior art that phthalimido percarboxylic acids if not stabilized degrade following a radical reaction pathway.
Without wishing to be bound to any theory, it is assumed that phthalimido
percarboxylic acids in fact degrade by attack of nucleophiles. A plausible degradation scheme of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) in alkaline conditions is shown in figure 1. According to figure 1 , PAP is degraded to 4- phthalimido-1-hexanol and carbon dioxide via an electrocyclic reaction. As a consequence, the presence of at least one lithium salt would prevent nucleophiles from degrading PAP either by excluding reactive nucleophiles, by blocking
nucleophilic reaction sites at PAP and/or by catching nucleophiles with electrophiles other than PAP.
Therefore, the present invention is directed to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
There is no restriction as concerns the chemical nature of the at least one lithium salt. Thus, the at least one lithium salt may be either organic or inorganic. Besides, the at least one lithium salt may be hydrous or anhydrous.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one inorganic lithium salt. The present
invention further relates to the mixture described above, characterized in that it comprises at least one organic lithium salt.
According to the present invention, it is preferred that the anion of the at least one lithium salt is rather non-nucleophilic. If the anion in question is too nuc!eophilic, it is assumed to compete against the lithium cation for interaction with the phthalimido percarboxylic acid. Suitable non-nucleophilic anions for use according to the present invention are hexafluorosilicate (SiF6 2"), sulfite (S03 2"), hydrogensulfite (HS03 ~), organosulfite (RS03 ~), sulfate (S04 2"), hydrogensulfate (HS04 "), organosulfate (RS04 "), phosphate (PO43 ), hydrogenphosphate (HPO42"). dihydrogenphosphate (H2P04 "), tetrafluoro borate (BF4 ~), tetrachloro borate (BCI4"), tetrabromo borate (BBr4_ ), tetraiodo borate (Bl4 "), tetraphenyl borate (B[C6H5]4"), tetra(pentafluoro)pheny! borate (B[C6F5]4"), hexafluorophosphate (PF6 ~), hexachloro aluminate (AICI6 3"), hexabromo aluminate {AIBr6 3'), corresponding anion of an organic acid {OC[0]R'), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof, wherein the sulfate anion represents the most preferred anion.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one lithium salt is selected from the group consisting of lithium hexafluorosilicate (L^SiFe), lithium sulfite (U2SO3), lithium hydrogensulfite (L1HSO3), lithium organosulfite (Li2RS03), lithium sulfate (Li2S04), lithium hydrogensulfate (LJHSO4), lithium organosulfate (LiRS04), lithium phosphate (Li3P04), lithium hydrogenphosphate {U2HPO4), lithium dihydrogenphosphate
(UH2PO4), lithium tetrafluoro borate (UBF4), lithium tetrachloro borate (LiBCI4), lithium tetrabromo borate (LiBB^), lithium tetraiodo borate (UBI4), lithium tetraphenyl borate (LiB[C6H5]4), lithium tetra(pentafluoro)phenyl borate (LiB[C6F5]4), lithium
hexafluorophosphate (LiPF6), lithium hexachloro aluminate (Li3AICI6), lithium hexabromo aluminate (Li3AIBr6), lithium salt of an organic acid (LiOC[0]R), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof. The present invention further relates to the mixture as described above, characterized in that it comprises lithium sulfate.
Also, there is no restriction as concerns the chemical nature of the at least one phthalimido percarboxylic acid. Suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the phthalimido
percarboxylic acids of the general formula (1), where n is an integer of from 1 to 5:
Thus, suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the group consisting of phthalimido peracetic acid (n=1 ), phthalimido perpropionic acid (n=2), phthalimido perbutyirc acid (n=3), phthalimido peramylic acid (n=4) and phthalimido percaproic acid (n=5), wherein phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP) represents the most preferred phthalimido percarboxylic acid.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one phthalimido percarboxylic acid selected from the phthalimido percarboxylic acids of the general formula (I) above, where n is an integer of from 1 to 5. The present invention further relates to the mixture described above, characterized in that it comprises phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP).
Phthalimido percarboxylic acids and especially phthalimido peroxycarproic acid may be prepared as described in EP 0 325 288 A1 and EP 0 349 940 B1 , respectively. Thus, a substrate selected from phthalimido carboxylic acids and anhydrides thereof having a structure corresponding to the desired percarboxylic acid, e.g. of the general formula (I), may be reacted with concentrated H2O2 in a reaction medium selected from concentrated H2S04 and CH3SO3H or in an alkaline medium, and the
percarboxylic acid is then separated from the reaction mixture by conventional and known techniques.
In order to obtain optimum stabilization of the at least one phthalimido percarboxylic acid, the content of lithium salt in the mixture should range between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10
% by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
Therefore, the present invention also relates to the mixture described above, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
Advantageously, the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
Therefore, the present invention also relates to the mixture described above, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1:1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
An especially expedient mixture for use as a bleaching agent comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
The mixture comprising the at least one phthalimido percarboxylic acid and the at least one lithium salt according to the present invention may be manufactured in the form of an aqueous solution, gel, emulsion, paste, dispersion, powder, flake, granules, scales, pearls, tablets, solid block form, extrudates and other forms known in the art, but preferably represents a powder or a flake.
Therefore, the present invention also relates to the mixture described above, characterized in that the mixture is in the form of a powder or a flake.
The mixture according to the present invention is particularly suitable as effective bleaching agent in detergent formulations.
Therefore, the present invention is also directed to the use of a mixture described above as a bleaching agent.
The present invention is further directed to a detergent composition comprising a mixture described above. The detergent composition may contain any additive or active ingredient commonly used in corresponding washing, cleansing and/or disinfecting agents like builders, surfactants, soaps, zeolites, hydrotropic agents, corrosion inhibitors, enzymes, optical brighteners, stabilizers, abrasives, perfumes, coloring agents.
The inventive mixture may be incorporated into the detergent composition either as such or in combination with further additives, for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc. in the forms mentioned above for the mixture.
It is preferred that the detergent composition is substantially free of boric acid, i.e. comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
Therefore, the present invention also relates to the detergent composition described before, characterized in that it comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
The detergent composition may be used as a laundry detergent, preferably as a textile detergent, and is not only suitable for generally washing laundry, but as well for disinfecting.
Besides, the detergent according to the present application may be used as cleanser and/or disinfectant for cleansing and disinfecting various kinds of hard surfaces like, for example, in the medicinal or institutional field, in the food preparing, processing and/or selling industry, in agriculture, in hotel business, catering trade and/or in public buildings and/or institutions. It may as well be useful in further applications in which a disinfected surface is required or desired and which are not explicitly mentioned herein. The surfaces supposed to become disinfected may be made of common
materials mentioned in the state of the art like, for example, metal, glass, ceramic, plastic, (coated) wood.
Finally, the present invention relates to the use of at least one lithium salt for stabilizing a phthalimido percarboxy!ic acid in a detergent composition.
In the following, the stabilization of phthalimido peroxycarboxylic acids with lithium salts will be demonstrated without being restricted to these examples.
EXAMPLES
Example 1 :
A mixture for use as a bleaching agent comprising 86 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and 14 % by weight of a stabilizing agent (example 1a: boric acid (comparative); example 1 b: sodium sulfate (comparative); example 1c: lithium sulfate) was tested for its long-term stability. Therefore, the amount of chemically active PAP in the respective mixture was determined after storage by 40 °C at 1 , 3, 7, 14, 21 , 28, 49, 84, 119, 161 and 2 0 days, respectively.
As can be taken from Table 1 , a mixture comprising lithium sulfate (example 1c) shows a significantly higher long-term stability of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) than a mixture comprising sodium sulfate (example 1b).
Table 1 :
Activity of PAP %
Claims
Claims
1. Mixture for use as a bleaching agent comprising at least one phthalimido
percarboxylic acid and at least one lithium salt.
2. Mixture according to claim 1 , characterized in that it comprises at least one inorganic lithium salt.
3. Mixture according to claim 1 or 2, characterized in that it comprises at least one organic lithium salt.
4. Mixture according to any of claims 1 to 3, characterized in that it comprises at least one lithium salt selected from the group consisting of lithium
hexafluorosilicate (Li2SiF6), lithium sulfite {U2SO3), lithium hydrogensulfite (LJHSO3), lithium organosulfite (Li2RS03), lithium sulfate (Li2S04), lithium hydrogensulfate (LiHS04), lithium organosulfate (L1RSO4), lithium phosphate (Li3P0 ), lithium hydrogenphosphate (Li2HP04), lithium dihydrogenphosphate (LiH2P04), lithium tetrafluoro borate (L1BF4), lithium tetrachloro borate (LiBCU), lithium tetrabromo borate (LiBBr ), lithium tetraiodo borate (LiBU), lithium tetraphenyl borate (LiBfCeHsk), lithium tetra(pentafluoro)phenyi borate
(LiB[C6F5]4), lithium hexafiuorophosphate (LiPFe), lithium hexachloro aluminate (Li3AICI6), lithium hexabromo aluminate (Li3AIBr6), lithium salt of an organic acid (LiOC[0]R), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl and combinations thereof.
5. Mixture according to any of claims 1 to 4, characterized in that it comprises lithium sulfate.
6. Mixture according to any of claims 1 to 5, characterized in that it comprises at least one phthalimido percarboxylic acid is selected from the phthalimido percarboxylic acids of the general formula (I)
7. Mixture according to any of claims 1 to 6, characterized in that it comprises phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP).
8. Mixture according to any of claims 1 to 7, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
9. Mixture according to any of claims 1 to 8, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
10. Mixture according to any of claims 1 to 9, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid
(phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
11. Mixture according to any of claims 1 to 10, characterized in that the mixture is in the form of a powder or a flake,
13. Detergent composition comprising the mixture according to any of claims 1 to 11.
14. Detergent composition according to claim 13, characterized in that it
comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
15. Use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES12725048.8T ES2595180T3 (en) | 2012-06-01 | 2012-06-01 | Stabilization of phthalimido percarboxylic acids with lithium salts |
| EP12725048.8A EP2855653B8 (en) | 2012-06-01 | 2012-06-01 | Stabilization of phthalimido percarboxylic acid with lithium salts |
| PCT/EP2012/060448 WO2013178289A1 (en) | 2012-06-01 | 2012-06-01 | Stabilization of phthalimido percarboxylic with lithium salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2012/060448 WO2013178289A1 (en) | 2012-06-01 | 2012-06-01 | Stabilization of phthalimido percarboxylic with lithium salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013178289A1 true WO2013178289A1 (en) | 2013-12-05 |
Family
ID=46201675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2012/060448 WO2013178289A1 (en) | 2012-06-01 | 2012-06-01 | Stabilization of phthalimido percarboxylic with lithium salts |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2855653B8 (en) |
| ES (1) | ES2595180T3 (en) |
| WO (1) | WO2013178289A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325288A1 (en) | 1988-01-20 | 1989-07-26 | AUSIMONT S.p.A. | Imido-aromatic percarboxylic acids |
| EP0349940B1 (en) | 1988-07-08 | 1998-05-13 | Clariant GmbH | Phthalimidohexanperacid, process for preparing the same and use thereof |
| EP1586628A1 (en) * | 2004-04-05 | 2005-10-19 | The Procter & Gamble Company | Particulate bleaching compositions |
| WO2006000344A1 (en) * | 2004-06-25 | 2006-01-05 | Henkel Kommanditgesellschaft Auf Aktien | Production of particle- shaped peroxycarboxylic acid compounds |
| WO2006120405A1 (en) * | 2005-05-09 | 2006-11-16 | Reckitt Benckiser N.V. | Detergent composition |
| JP2010138268A (en) * | 2008-12-11 | 2010-06-24 | Kao Corp | Liquid bleaching detergent composition |
-
2012
- 2012-06-01 ES ES12725048.8T patent/ES2595180T3/en active Active
- 2012-06-01 EP EP12725048.8A patent/EP2855653B8/en active Active
- 2012-06-01 WO PCT/EP2012/060448 patent/WO2013178289A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325288A1 (en) | 1988-01-20 | 1989-07-26 | AUSIMONT S.p.A. | Imido-aromatic percarboxylic acids |
| EP0349940B1 (en) | 1988-07-08 | 1998-05-13 | Clariant GmbH | Phthalimidohexanperacid, process for preparing the same and use thereof |
| EP1586628A1 (en) * | 2004-04-05 | 2005-10-19 | The Procter & Gamble Company | Particulate bleaching compositions |
| WO2006000344A1 (en) * | 2004-06-25 | 2006-01-05 | Henkel Kommanditgesellschaft Auf Aktien | Production of particle- shaped peroxycarboxylic acid compounds |
| WO2006120405A1 (en) * | 2005-05-09 | 2006-11-16 | Reckitt Benckiser N.V. | Detergent composition |
| JP2010138268A (en) * | 2008-12-11 | 2010-06-24 | Kao Corp | Liquid bleaching detergent composition |
Non-Patent Citations (2)
| Title |
|---|
| CHEM. IND., 1961, pages 469 |
| J. CHEM. SOC., 1962, pages 3821 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2595180T3 (en) | 2016-12-28 |
| EP2855653B8 (en) | 2016-12-07 |
| EP2855653B1 (en) | 2016-07-20 |
| EP2855653A1 (en) | 2015-04-08 |
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