MXPA99006945A - Photochemical superoxide generators - Google Patents
Photochemical superoxide generatorsInfo
- Publication number
- MXPA99006945A MXPA99006945A MXPA/A/1999/006945A MX9906945A MXPA99006945A MX PA99006945 A MXPA99006945 A MX PA99006945A MX 9906945 A MX9906945 A MX 9906945A MX PA99006945 A MXPA99006945 A MX PA99006945A
- Authority
- MX
- Mexico
- Prior art keywords
- mixtures
- branched
- alkyl
- substituted
- alkenyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims abstract description 305
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 47
- 230000002165 photosensitisation Effects 0.000 claims abstract description 40
- 238000004140 cleaning Methods 0.000 claims abstract description 38
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 239000003599 detergent Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 152
- 125000003342 alkenyl group Chemical group 0.000 claims description 109
- 125000004104 aryloxy group Chemical group 0.000 claims description 68
- 229910052739 hydrogen Inorganic materials 0.000 claims description 66
- 239000001257 hydrogen Substances 0.000 claims description 66
- 125000003545 alkoxy group Chemical group 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 150000002431 hydrogen Chemical class 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 125000002947 alkylene group Chemical group 0.000 claims description 40
- -1 ethyleneoxy Chemical group 0.000 claims description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 125000003107 substituted aryl group Chemical group 0.000 claims description 34
- 150000001768 cations Chemical class 0.000 claims description 31
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 30
- 125000005237 alkyleneamino group Chemical group 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 125000004429 atoms Chemical group 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000004744 fabric Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 125000005275 alkylenearyl group Chemical group 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 125000004450 alkenylene group Chemical group 0.000 claims description 13
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 239000002738 chelating agent Substances 0.000 claims description 12
- 125000004001 thioalkyl group Chemical group 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical group [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003981 vehicle Substances 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 230000000249 desinfective Effects 0.000 claims description 5
- 150000002829 nitrogen Chemical class 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 102000004190 Enzymes Human genes 0.000 claims description 4
- 108090000790 Enzymes Proteins 0.000 claims description 4
- 229910006067 SO3−M Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Chemical group 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 230000027455 binding Effects 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003082 abrasive agent Substances 0.000 claims description 2
- 239000011538 cleaning material Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 125000004171 alkoxy aryl group Chemical group 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N Anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- 125000005577 anthracene group Chemical group 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- 125000003302 alkenyloxy group Chemical group 0.000 claims 1
- 230000000735 allogeneic Effects 0.000 claims 1
- BICAGYDGRXJYGD-UHFFFAOYSA-L bromide;chloride Chemical group [Cl-].[Br-] BICAGYDGRXJYGD-UHFFFAOYSA-L 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000005755 formation reaction Methods 0.000 abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M CHEMBL593252 Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- RDFLLVCQYHQOBU-GPGGJFNDSA-O Cyanin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@H](CO)O1)c1c(-c2cc(O)c(O)cc2)[o+]c2c(c(O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O3)cc(O)c2)c1 RDFLLVCQYHQOBU-GPGGJFNDSA-O 0.000 description 10
- LKKPNUDVOYAOBB-UHFFFAOYSA-N Naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atoms Chemical group C* 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 235000019864 coconut oil Nutrition 0.000 description 5
- 239000003240 coconut oil Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- IIMIOEBMYPRQGU-UHFFFAOYSA-L Picoplatin Chemical compound N.[Cl-].[Cl-].[Pt+2].CC1=CC=CC=N1 IIMIOEBMYPRQGU-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000005526 alkyl sulfate group Chemical group 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000005281 excited state Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000000844 anti-bacterial Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M Potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M Potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- IKEIGECHKXPQKT-UHFFFAOYSA-N Silicon phthalocyanine dihydroxide Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[Si](O)(O)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 IKEIGECHKXPQKT-UHFFFAOYSA-N 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N Silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K Tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- SPFMVVNPVIZTBL-UHFFFAOYSA-N [Si].N(CCO)(CCO)CCO.N(CCO)(CCO)CCO Chemical compound [Si].N(CCO)(CCO)CCO.N(CCO)(CCO)CCO SPFMVVNPVIZTBL-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M carbamate Chemical class NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L mgso4 Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000002987 phenanthrenes Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L phosphate Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000001737 promoting Effects 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001603 reducing Effects 0.000 description 2
- 230000002441 reversible Effects 0.000 description 2
- 238000011012 sanitization Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- 125000006835 (C6-C20) arylene group Chemical group 0.000 description 1
- MPJQXAIKMSKXBI-UHFFFAOYSA-N 2,7,9,14-tetraoxa-1,8-diazabicyclo[6.6.2]hexadecane-3,6,10,13-tetrone Chemical compound C1CN2OC(=O)CCC(=O)ON1OC(=O)CCC(=O)O2 MPJQXAIKMSKXBI-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-J 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O KCXVZYZYPLLWCC-UHFFFAOYSA-J 0.000 description 1
- XPTYFQIWAFDDML-UHFFFAOYSA-N 2-aminoacetic acid;ethanol Chemical class CCO.NCC(O)=O.NCC(O)=O XPTYFQIWAFDDML-UHFFFAOYSA-N 0.000 description 1
- RJFAMAFEWDBSLX-UHFFFAOYSA-N 3,6-dibutoxybenzene-1,2-dicarbonitrile Chemical compound CCCCOC1=CC=C(OCCCC)C(C#N)=C1C#N RJFAMAFEWDBSLX-UHFFFAOYSA-N 0.000 description 1
- KWYJDIUEHHCHCZ-UHFFFAOYSA-J 3-[2-[bis(2-carboxylatoethyl)amino]ethyl-(2-carboxylatoethyl)amino]propanoate Chemical class [O-]C(=O)CCN(CCC([O-])=O)CCN(CCC([O-])=O)CCC([O-])=O KWYJDIUEHHCHCZ-UHFFFAOYSA-J 0.000 description 1
- IOYBLYAUPGRGAS-UHFFFAOYSA-N 3-butoxybenzene-1,2-dicarbonitrile Chemical compound CCCCOC1=CC=CC(C#N)=C1C#N IOYBLYAUPGRGAS-UHFFFAOYSA-N 0.000 description 1
- JAWNWEKHDFBPSG-UHFFFAOYSA-N 3-iminobenzo[f]isoindol-1-amine Chemical compound C1=CC=C2C=C3C(N)=NC(=N)C3=CC2=C1 JAWNWEKHDFBPSG-UHFFFAOYSA-N 0.000 description 1
- SRIJSZQFAMLVQV-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-dicarbonitrile Chemical compound ClC1=CC(C#N)=C(C#N)C=C1Cl SRIJSZQFAMLVQV-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N 4-chloro-N-[(propylamino)carbonyl]benzenesulfonamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- MGRVRXRGTBOSHW-UHFFFAOYSA-N Aminomethylphosphonic acid Chemical class NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 240000007170 Cocos nucifera Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OVGXLJDWSLQDRT-UHFFFAOYSA-L Magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N Porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005025 alkynylaryl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000000845 anti-microbial Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 201000004002 aromatase excess syndrome Diseases 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 201000008220 erythropoietic protoporphyria Diseases 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-M ethyl carbonate Chemical class CCOC([O-])=O CQDGTJPVBWZJAZ-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940071087 ethylenediamine disuccinate Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 210000001357 hemopoietic progenitor cell Anatomy 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940087748 lithium sulfate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000000626 magnesium lactate Substances 0.000 description 1
- 235000015229 magnesium lactate Nutrition 0.000 description 1
- 229960004658 magnesium lactate Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- KNBYJRSSFXTESR-UHFFFAOYSA-N naphthalene-2,3-dicarbonitrile Chemical compound C1=CC=C2C=C(C#N)C(C#N)=CC2=C1 KNBYJRSSFXTESR-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-K nitrilotriacetate(3-) Chemical class [O-]C(=O)CN(CC([O-])=O)CC([O-])=O MGFYIUFZLHCRTH-UHFFFAOYSA-K 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000005298 paramagnetic Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- RWMKKWXZFRMVPB-UHFFFAOYSA-N silicon(4+) Chemical compound [Si+4] RWMKKWXZFRMVPB-UHFFFAOYSA-N 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VQOIVBPFDDLTSX-UHFFFAOYSA-M sodium;3-dodecylbenzenesulfonate Chemical class [Na+].CCCCCCCCCCCCC1=CC=CC(S([O-])(=O)=O)=C1 VQOIVBPFDDLTSX-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000003381 solubilizing Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001180 sulfating Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000011778 trisodium citrate Substances 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Disclosed are photochemical super oxide generators useful as photobleaches for laundry detergent compositions and as photobleaches or photodisinfectants for use in hard surface cleaning compositions. The compounds described herein comprise an amino-containing electron transfer moiety bonded to the photosensitizing unit wherein the amino-containing moiety is capable of transfering an electron to the photochemically excited&pgr;electron cloud of the photosensitizer unit thereby enabling superoxide formation.
Description
SUPEROXID PHOTOCHEMICAL GENERATORS
FIELD OF THE INVENTION
The present invention relates to photochemical superoxide generators and their use in laundry compositions and hard surface cleaning compositions consisting of one or more of said photochemical superoxide generators, effective as bleaching agents, stain removers or bactericides. The present invention also relates to methods for cleaning fabrics or hard surfaces, and for providing means of sanitizing fabrics or hard surfaces.
BACKGROUND OF THE INVENTION
It is known that certain water-soluble compounds of phthalocyanine, naphthalocyanine, mixed cyanine and metallocyanine can be used as photobleaching and antimicrobial agents. Phthalocyanines, naphthalocyanines or their metal complexes can form "singlet oxygen", an oxidizing species capable of reacting with bleaching spots to a colorless state and normally soluble in water. It has been surprising to find that certain compounds of porphyrin, metalloporphyrin, phthalocyanine, naphthalocyanine, mixed cyanine, and metallocyanin can produce photochemically superoxide. Superoxide is typically formed via non-photochemical means from the disproportionation of superoxide alkaline and alkaline earth metals. Superoxide is a kind of reactive oxygen formed by the reduction of an electron of oxygen, has a life time greater than oxygen in singlet and is able to discolor (bleach) spots and kill bacteria. Throughout this description superoxide is presented as O2-based on the practice of common literature. Surprisingly, it has been discovered that superoxide can be efficiently produced by photochemical means. Some photosensitizing units that consist of a portion capable of transferring an electron to the cloud of photochemically excited electrons of the photosensitizing unit are capable of producing superoxide. Preferably the photosensitizers, preferably porphyrins, metalporphyrins, harmful, and metallocyanines, and have the electron transfer portion covalently attached. Therefore, it is an aspect of the present invention to provide new materials that photochemically produce superoxide. These materials are photosensitization units that have covalently attached a portion capable of transferring an electron to the excited state of the aforementioned photosensitizer. The superoxide produced by these compounds is useful since the superoxide molecules are capable of acting as bleaching materials or as antimicrobials.
Another aspect of the present invention is to provide detergent compositions for laundry and hard surface cleaning consisting of the aforementioned superoxide generators. In accordance with another aspect of the present invention, a method for removing cloth stains and for killing bacteria as well as preventing the re-propagation of said bacteria is provided herein. The method consists of contacting the fabrics or surface contaminated with the bacteria with an aqueous medium consisting of at least 0.001 ppm of the photochemical superoxide generators described herein below. These, and other objects, features, and advantages will be clear from the following detailed description and appended claims.
TECHNICAL BACKGROUND
The following references relate to various aspects of the superoxide and photochemical processes that are included in the present invention: Chem. Rev., Kavamos G.J., Turro N.J., 86, pg.401, (1986); Angew. Chem. Int. Ed. Eng., Mattay J., 26, pg.825, (1987); Adv. Phys. Org. Chem., Eberson L., 18, pg. 79, (1987); Top. Current Chem., López, L., 156, pg, 117 (1990); Adv. Photochem, Fox, M.S., 13, pg.237, (1986); "Synthetic Organic Photochemistry", Horspool W.M. (ed); Mariano, P.S., pg.145, (1984), Plenum Press, New York; Organic Photochemistry, "Padwa, A. (ed), Mattes, S.L. and Farid, S., 6, pp. 233, (1983); Accounts of Chemical Research, Parker, V.D., 17, p.243, (1984).
BRIEF DESCRIPTION OF THE INVENTION 5 The present invention relates to photochemical superoxide generators having the formula
D D I. I p o p I I 10 D R
where P is a photosensitizing group; each D is independently a unit that has the formula: L1 - E or L1 B [L2- E] m where B is a unit capable of providing a branch point; L1 and L2 are 15 link units; the E units are electron transfer units that have the formula:
Wherein each W1 and W2 is independently C1-C4 alkylene, G is hydrogen, an electron separation group, and mixtures thereof, m is from 2 to 4; since: a) L1, L2 and B alone or in combination do not form continuous series of conjugated bonds extending from the photosensitizing group P to the E portion; and b) The number of chemical bonds of the photosensitizing group P to unit E is not more than 20; and R is an axial portion that regulates the solubility or substantivity of the superoxide generator. It is also an object of the present invention to provide laundry detergent compositions consisting of photochemical superoxide generators described herein and methods for using said superoxide generators to whiten fabric. Laundry detergent compositions comprise: a) at least about 0.1% by weight, of a detersive surfactant; b) at least about 0.001% of a source of superoxide; and c) the remaining vehicles and auxiliary ingredients. Another object of the present invention is to provide cleaning compositions for hard surfaces and a method of sanitizing a hard surface by contacting the superoxide generators described herein with a surface that needs to be cleaned or disinfected.
Still another object of the present invention is to provide a method for bleaching fabric having dirt or stains, or when bleaching is needed, by contacting an aqueous solution of photochemical superoxide generators of the present invention with said fabric. 5 All percentages, ratios and proportions in this document are given by weight, unless otherwise specified. All temperatures are given in degrees Celsius (° C) unless otherwise specified. All the cited documents are a relevant part, and they are incorporated into this document by reference. 10 DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to superoxide generators where the superoxide is induced by photochemical means, that is, the superoxide is produced when the superoxide generators are exposed to a light source. The resulting superoxide molecule that is generated in this way has the ability to act as an effective bleaching agent, disinfectant or bactericide. The superoxide generators of the present invention have the formula:
D D I, I P o p I I
D R
and consist of: a) a photosensitizing group; b) optionally a metal or non-photoactive metal; c) at least one portion capable of transferring an electron to the excited state of the photosensitizing group; and 5 d) optionally an axial portion that regulates the solubility or substantivity of the superoxide generating molecule. For the purposes of the present invention the substituted aryl units are defined as portions having the formula:
wherein R13 and R14 are independently selected from the group consisting of hydrogen, CrC6 alkyl, C2-C6 alkenyl, C-? -C6 alkoxy,
C3-C6 branched alkoxy, halogen, morfoiino, cyano, nitrile, -CO2"M +, -SOs'IVT, -OS03" M +, -N (R15) 2 and -N + (R15) 3X ", where each R15 is independently hydrogen or C 1 -C 4 alkyl and mixtures thereof, wherein M is a water soluble cation and X is chlorine, bromine, iodine, or other water soluble anion Examples of other water soluble anions include
organic species such as fumarate, tartrate, oxalate and the like, inorganic species include sulfate, hydrogen sulfate, phosphate and the like. For the purposes of the present invention the substituted alkylene ring units are defined as portions having the formula: wherein R13 and R14 are the same as those defined above, p is from 1 to about 10. For the purposes of the present invention the units substituted aryloxy are defined as portions having the formula:
wherein R13 and R14 are as defined above. For the purposes of the present invention substituted alkyleneoxyaryl units are defined as portions having the formula:
wherein R13 and R14 are the same as defined above, q is from 0 to about 10. For the purposes of the present invention, substituted oxyalkylene units are defined as portions having the formula:
where R13 and R14 are as defined above, w is from 1 to about 10. For the purposes of the present invention, both substituted and unsubstituted arynes, alkylenedyls, aryloxy, and oxyalkylenoxyls have the indices p. q, and w as defined above. For purposes of the purposes of the present invention, substituted alkyl units are defined as portions having the formula
- (A) v-HCH2) VZ
where A is the heterogeneous atom of nitrogen or oxygen, preferably A is oxygen, the index v is 0 when the heterogeneous atom is absent, v is equal to 1; when the heterogeneous atom is present, Z is hydroxyl, nitrile, cyano, Ci-Cβ alkoxy, aryio, substituted aryl, aryloxy, and substituted aryloxy as defined above; alkyleneamino as hereinafter defined, hydroxyl, -SO3-M +, -OSO3-M +, -CO2H, -N (R15) 2, and mixtures thereof; each R15 is independently hydrogen or C1-C4 alkyl, C1-C4 hydroxyalkyl; M is a cation soluble in water; and it's from 0 to 22.
For the purposes of the present invention the alkylethylaxy units are defined as portions having the formula:
- (A) v- (CH2) and (OCH2CH2)? Z
where A is the heterogeneous atom of nitrogen or oxygen, preferably A is oxygen, the index v is 0 when the heterogeneous atom is absent, v is equal to 1 when the heterogeneous atom is present, Z is hydrogen, C? -C6 alkoxy , ary, substituted aryl, aryloxy, substituted aryioxy, alkyleneamino, SO3-M +, -OS03M +, -CO2H, and mixtures thereof; x is from 1 to 100, and y is from 1 to 12.
For the purposes of the present invention the alkyleneamino units are defined as portions having the formula: R 1 or I - (A - (CH 2) u- + - R 2 X "R 11
wherein R10 and R11 are each a C? -C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, R12 is hydrogen, C? Branched C3-C22, C2-C22 alkenyl, branched C3-C22 alkenyl and mixtures thereof, A is the heterogeneous nitrogen or oxygen atom, preferably A is oxygen, the index v is 0 when the heterogeneous atom is absent, v is equal to 1 when the heterogeneous atom is present, X is chlorine, bromine, iodine, or other water-soluble anion, or is from 0 to 22. Examples of other water-soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include sulfate, hydrogen sulfate, phosphate and the like. For the purposes of the present invention the amino units are defined as portions having the formula:
NR17R18
wherein R17 and R18 are each a C? -C22 alkyl, C3-C22 alkyl
branched, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof. For the purposes of the present invention the linear or branched C- - -C20 alkylene portions are defined as units having the formula: R16
(CH2) i (CH) j where R16 is a C1-C4 alkyl; the index i has the value of 1 to 18, the index j has the value of 1 to 18, and the value of i + j can not exceed 18. For purposes of the present invention the alkenylene portions of linear CiC-is or branched are defined as portions that consist of one or more units, or combinations of units that have the formula: R16 I [CH = CH- (CH2) j] j - or - [CH = C- (CH2) j] j - or
where R16 is C1-C4 alkyl; the index i has the value of 1 to 14, the index j has the value of 1 to 6, since the number of covalent bonds in the structure, excluding the links that consist of R16, do not exceed 18.
For purposes of the present invention, linear or branched C1-C18 alkyleneoxy moieties consisting of units L1 or L2 described hereinafter are defined as units or a combination of units having the formula:
where R16 is C1-C4 alkyl, the index x has a value of 2 to 4; i has the value of 1 to 6, the index j has the value of 1 to 6, the index k has the value of 1 to 6, and the value of i + j + k can not exceed 6 if x equals 2; if x is greater than 2 the number of bonds consisting of the alkyleneoxy moiety can not exceed 18. For the purposes of the present invention the arylene portions of substituted or unsubstituted C? -C? 8 are defined as units 1, 2-phenylene, 1,3-phenylene, and 1,4-phenylene having the formula:
where R16 is hydrogen, C1-C4 alkyl, and mixtures thereof. For the purposes of the present invention, the alkylenelene portions of substituted or unsubstituted C-rds are defined as 1,2-phenylene, 1,3-phenylene and 1,4-phenylene units having the formula: wherein R > 16 is hydrogen, C 1 -C 4 alkyl, and mixtures thereof, the index p having the value of 1 to 12. For the purposes of the present invention, the aryneoxy portions of C 1 -C 8 substituted and unsubstituted are defined as 1, 2-phenyleneoxy, 1,3-phenylenoxy and 1,4-phenyleneoxy units having the formula:
where R16 is hydrogen, C? -C4 alkyl, and mixtures thereof. For purposes of the present invention, the substituted and unsubstituted C-i-C-is substituted oxyalkylenenane moieties are defined as 1,2-oxyalkylenephenylene, 1,3-oxyalkylenephenylene, and 1,4-oxyalkylenephenylene units having the formula:
where R > 1 '6 is hydrogen, C 1 -C 4 alkyl and mixtures thereof, the index w have the value from 1 to 11.
For purposes of the present invention, the substituted and unsubstituted C1-C18 alkylarylene xylene moieties are defined as 1,2-alkylenedioxyphenylene, 1,3-alkyleneoxypheniene, and 1,4-alkylene oxyphenylene units having the formula:
wherein R16 is hydrogen, C1-C4 alkyl, and mixtures thereof, the index q has a value of 1 to 11.
Photosensitizing groups The superoxide generators of the present invention contain a photosensitizing group. The preferred photosensitizing groups P are the harmful ones and metallocyanines. The photosensitizing groups of cyanine include phthalocyanines, naphthalocyanines, mixed harmful, as well as other aromatic photosensitizing units described below. Preferably the photosensitizing groups are combined with a photoactive metal or non-metal to produce a metallocyanine photosensitizer. However, the photosensitizing groups of the present invention must be capable of being electrochemically reduced, ie they must be capable of receiving an electron from the "electron transfer unit" E described herein.
When the photosensitizing group P is a cyanine ring, said ring has the formula:
Wherein rings A, B, C and D are aromatic rings independently selected from the group consisting of substituted and unsubstituted benzene, substituted and unsubstituted naphthalene, substituted and unsubstituted anthracene, substituted and unsubstituted phenanthrene, and mixtures thereof . For the purposes of the present invention the components
of the substituted and unsubstituted benzene derivative cyanine ring can be written in any of the two equivalent resonance formulas:
twenty
wherein R1, R2, R3 and R4 are each independently selected from the substituents described hereinafter. For the purposes of the present invention, the cyanine ring components derived from substituted and unsubstituted 2,3-naphthylene can be written in any of the two equivalent resonance formulas:
where R1, R2, R3, R4, R5 and R6 are independently selected from the substituents described hereinafter. For the purposes of the present invention, the cyanine ring components derived from substituted and unsubstituted 1, 2-naphthylene can be written to any of the two equivalent resonance formulas:
wherein the units R1, R2, R3, R4, R5 and R6 are independently selected from the substituents listed below. For the purposes of the present invention, the cyanine ring components derived from substituted and unsubstituted anthracene can be written in any of the two equivalent resonance formulas:
wherein the units R1, R2, R3, R4, R5, R7 and R8 are independently selected from the substituents described hereinafter. For the purposes of the present invention, the cyanine ring components derived from substituted and unsubstituted phenanthrene can be written to any of the two equivalent resonance formulas: where the units R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from the substituents described below in the present invention. For the purposes of the present invention each unit R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from the group consisting of: a) hydrogen; 15 b) halogen; c) hydroxy; d) C? -C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenylene, branched C3-C22 alkenyl, or mixtures thereof; 20 e) halogen-substituted C-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; f) C3-C22 polyhydroxy-substituted alkyl;
g) akoxy of C C22; h) branched alkoxy having the formula:
or
wherein Z is hydrogen, hydroxyl, CrC30 alkyl, C1-C30 alkoxy, -CO2H, -OCH2CO2H, -SO3-M +, -OSO3-M +, -PO32"M, -OPO32" M or mixtures thereof; M is a cation soluble in water in an amount sufficient to satisfy the equilibrium of the charge; x is 0 or 1, each y independently having the value from 0 to 6, preferably 0 to 6; each z independently has the value from 0 to 100; i) substituted aryl, unsubstituted aryl or mixtures thereof; j) substituted alkylenearyl, unsubstituted alkynylaryl or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof;
I) unsubstituted substituted oxyalkylenearyl, oxyalkylenearyl or mixtures thereof; m) substituted alkylenenoxy and unsubstituted alkyleneoxyaryl, or mixtures thereof; n) thioalkium of C? -C22, branched C3-C22 thioaikyl, or mixtures thereof; or) an ester of the formula -CO2R9 wherein R9 is: i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof ii) alkyl of C? -C22 substituted with halogen; branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenniium, or mixtures thereof; iii) C3-C22-substituted polyhydroxyl-alkylene, iv) C3-C22-glycol; v) C? -C22 alkoxy, vi) branched C3-C22 alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;
x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; xi) substituted alkynoxyaryl, alkylenoxyaryl not
substituted, or mixtures thereof; p) an alkyleneamino unit of formula:
wherein R10 and R11 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkennio, branched C3-C22 alkenyl, or mixtures thereof; R12 is: i) hydrogen, ii) CrC22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl. C3-C22 branched alkenyl and mixtures thereof; A is nitrogen or oxygen; X is chlorine, bromine, iodine, or other water-soluble anion, v is 0 or 1, u is from 0 to 22; q) an amino unit of the formula:
NR17R18 where R17 and R18. they are C1-C22 alkyl. branched C3-C2 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit with the formula:
(A) v (CH2) and (OCH2CH2) Z wherein Z is: i) hydrogen, ii) hydroxyl, iii) -CO2H, iv) -SO3"M \ v) -OSO" M +, vi) CrC6 alkoxy , vii) substituted aryl, non-substituted ary, or mixtures of these; viii) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; X) alkyleneamines or mixtures thereof thereof; A is nitrogen or oxygen; M is a cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12, s) substituted siloxy of the formula: -OSiR19R20R21, wherein each R19, R20 and R21 is independently i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl. C3-C22 branched alkenyl or mixtures thereof; ii) substituted aryl, non-substituted ary, or mixtures thereof;
iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
(A) v (CH2) and (OCH2CH2) XZ
wherein Z is: a) hydrogen, b) hydroxyl, c) -CO2H; d) -SO3'M +, e) -OSO3"M +, f) C6-C6 alkoxy, g) substituted aryl, unsubstituted aryl, or mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; i) alkyleneamines or mixtures thereof, A is nitrogen or oxygen, M is a water-soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12, or mixtures thereof; P ring limiter photosensitizer is the unsubstituted phthalocyanine moiety that has the formula:
where the units R1, R2, R3, and R4 of each benzene ring is a hydrogen atom. Another example of the photosensitizing ring P is the unsubstituted portion 2,3-naphthalocyanine having the formula:
where the units R1, R2, R3, R4, R5 and R6 of each naphthylene ring is a hydrogen atom. However, the photosensitizing ring may consist of more than one type of substituted or unsubstituted units. This mixture of units results in the formation of a photosensitizing group of hybrid cyanine. A non-limiting example of a "hybrid cyanine" or "mixed cyanine" ring system is the unsubstituted ring of (3) -benzene- (1) -naphthalene having the formula:
wherein the units R1, R2, R3, and R4 of each of the benzene rings is a hydrogen atom, and the units R1, R2, R3, R4, R5 and R6 of the naphthylene ring is a hydrogen atom. The term "hybrid cyanine" is taken to include all reaction products that are formed when two or more monomers react together. Those skilled in the art will recognize that the resulting mixture also contains non-hybrid structures, however, for the purposes of the present invention these non-hybrid structures are comprised within the definition of "hybrid cyanins". It must also be recognized that as the number of different monomers increases, the number of possible hybrid rings formed also increases. As indicated above, "hybrid cyanins" can be formed by reacting two or more different monomers. In addition, the stoichiometric ratio of these monomers may vary. The following are non-limiting examples of reactions to form mixed cyanines.
where the ratio of the indices x and y indicate the stoichiometric quantities of each reactable material, said reactable material ratios can vary from 0.01 to 100, this means that the value of x can be 1 when the value of y is 100 and the value of x it can be 100 when the value of y is 1. The following formula
is a main product from the following stoichiometry reaction
Preferably the hybrid cyanins and cyanines are combined with a metal or non-photoactive metal. Metal or non-metal "photoactive" refers to any atom that when combined with a photosensitizing unit according to the present invention drives the photophysics of the photosensitizing unit. Preferred photoactive metals and non-metals include, but are not limited to, silicon, aluminum, phosphorus, tin, germanium, platinum, palladium, lead, cadmium, zinc, and mixtures thereof. However, any metal or non-photoactive metal is suitable for use in combination with the photosensitizing groups of the present invention, provided that said metal or non-photoactive metal has a valence of at least greater than 3. The metals and non-metals that are not suitable for use in the present invention are the paramagnetic atoms among others, iron, copper, chromium and cobalt. Another suitable photosensitizing group is porphyrins and metalloporphyrins having the formula:
where R 'is aryl, substituted ary, and mixtures thereof, as defined above.
Electron transfer portion The photochemical superoxide generators of the present invention must contain an Electron Transfer Portion. For the purposes of the present invention the term "electron transfer portion" is defined as "a portion that is capable of transferring an electron to a photosensitizing group P when the photosensitizer is in an excited state". Put in other terms, the transfer of an electron from the transfer portion to the photochemically excited state of the photosensitizing group is a key procedure for the production of superoxide. This electron transfer procedure is normally performed in a very fast and reversible procedure. However, for the E units of the present invention this transfer is not reversible. Without expecting to be bound by theory, when an electron is transferred by an "electron transfer unit" as described in this document, unit E is modified in such a manner (typically by chemical fragmentation) that unit E can not return to accept the transferred electron and therefore the procedure is a one-way transfer. The donor portion is decomposed before transferring the electron again. Once the transfer is complete the superoxide formation ensues. When all the "electron transfer units" are depleted, the remaining photoactive material is still capable of producing "singlet oxygen", another type of bleaching agent or photochemical disinfectant. In accordance with the present invention the electron transfer portions are included in an electron transfer unit E and a suitable unit for linking the unit E to the photosensitizing unit P. The electron transfer portions have the formula:
-L -E L1- B- [L2-E] m
where L1 and L2 are binding units and B is an atom capable of providing 2 to 4 branching points. The index m has the value of 2 to 4. The units B have the following formulas:
wherein preferably B is selected from the group consisting of boron, aluminum, nitrogen, phosphorus, carbon, silicon, tin, germanium, and mixtures thereof, most preferably carbon, silicon and nitrogen. L1 and L2 are linking units where L1 and each L2 are independently selected from the group consisting of oxygen, linear or branched CiC-iß alkylene, linear or branched C1-C18 alkenylene, substituted or unsubstituted C1-C18 alkylenoxy, C 1 -C 18 substituted or unsubstituted arylene, substituted or unsubstituted C 1 -C 18 alkylenearylene, substituted or unsubstituted C 1 -C 18 aryleneoxy substituted or unsubstituted C 1 -C 18 oxyalkylenearylene, alkyleneoxyarylene, and mixtures thereof, said Units are defined earlier in this document.
For the purposes of the present invention an oxygen molecule can serve as a suitable L1 unit, preferably when directly linked to a branched unit to form a portion having the general formula:
The E units are electron transfer units that have the formula:
where each W1 and W2 is C1-C4 alkyi independently. G is hydrogen, an electron separation group, and mixtures thereof, preferably G is selected from the group consisting of halogen, nitro, cyano, substituted or unsubstituted phenyl, hydroxyl, alkoxy, -CO2R29, -CO2M, - SO3M, -OS03M, -PO3M, -OPO3M, -CON (R29) Z where R29 is hydrogen, C-1-C12 alkyl, alkyleneoxy units having the formula:
where R28 is CrC4 alkyl, Z is hydrogen, C1-C22 alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkyleneamino, -SO3"M +, -OSO3" M +, - CO2H, and mixtures thereof; the index x has the value of 1 to 4, and has the value of 0 to 20, the index j has the value of 0 to 20, the index k has the value of 0 to 20, the alkyleneamino units have the formula:
where R10 and R1 are each C? -C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, R12 is hydrogen, C1-C22 alkyl, C3-C22 alkyl branched, C2-C22 aicynyl, branched C3-C22 alkenyl and mixtures thereof, A is a heterogeneous nitrogen or oxygen atom, preferably A is oxygen, the index v equals 0 when the heterogeneous atom is absent, v is equal to 1 when the heterogeneous atom is present, x is chloride, bromide, iodide or other water-soluble anion, or is from 0 to 22, most preferably G is: a) C 1 -C 6 alkoxy; b) hydroxyl; c) -CO2R29; d) -CO2M; e) -SO3M; f) ethyleneoxy of the formula:
- (OCr ^ Cr ^ xZ where Z is: i) hydrogen; ii) hydroxyl; Ii) C? -C22 alkoxy; iv) -CO2M; v) -CH2CO2M vi) -SO3M; vii) -OSO3M; or viii) alkyleneamino; M is hydrogen, a water soluble cation or mixtures thereof, x is from 1 to 20. The value of the index m depends on the nature of the branching of unit B and can have the value of 2 to 4, preferably 3. The electron transfer portions of the present invention should not have more than twenty links between the point of attachment to the photosensitizing unit and the point of attachment to the electron transfer unit E, and the links contain the link between the portion amino and P photosensitizer group should not contain a series of conjugated bonds. In other words; "L1, L2 and B alone or in combination do not form a continuous series of conjugated bonds extending from the photosensitizing group P to the portion E and the number of chemical bonds from the photosensitizing group P to the nitrogen portion are no more than 20 in number. "
The following are non-limiting examples of electron transfer portions suitable for use in the present invention. An example is given below where L1 is a linear alkylene unit and consists of six non-conjugated bonds between the photosensitizing group P and the unit E; E is a dihydroxyalkylamine where W1 and W2 each are hydroxyethyl, which have the formula:
An example is given below where L1 is an alkylenoxy unit consisting of 3 ethyleneoxy units, B is a branching point of methine carbide, each L2 is ethylene, the units L1, L2 and B together consist of thirteen non-conjugated bonds between the photosensitizing group P and the unit E; E is a dihydroxyalkylamine where W1 and W2 each are hydroxyethyl, of the formula:
Axial units R The superoxide photochemical generators of the present invention optionally consist of axial units R covalently linked to the central metal atom, where each R is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) C 1 -C 2 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof; f) C 1 -C 22 alkyl substituted with halogen, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof; g) C3-C22 alkyl substituted with polyhydroxyl h) C1-C22 akoxy i) branched alkoxy of the formula
CH (OMCHzJyíOCHaCHzfe - CH2 (OJxfCHaJyíOCHzCHzfe • where Z is hydrogen, hydroxyl, C? -C30 alkyl, C1-C30 alkoxy, -CO2H, -OCH2CO2H, -SO3"M +, -OSO3" M +, -PO32"M, -OPO32"M, and mixtures thereof, M is a cation soluble in water in sufficient quantity to satisfy the charge equilibrium, x is 0 or 1, each and independently has the value of 0 to 6, preferably 0 to 6, each z independently has the value from 0 to 100, preferably from 0 to about 10, most preferably from 0 to about 7; j) substituted aryl, unsubstituted aryl, or mixtures thereof, k) substituted alkylenearyl, unsubstituted alkylenearyl or mixtures of these. I) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; m) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; n) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; o) CrC22 thioalkyl, substituted C3-C22 thioalkyl, and mixtures thereof; p) Aquilekylene amino units; q) An amino unit of the formula - NR17R18 wherein R17 and R18 consist of 0-22 alkyl, branched C3-C22 alkyl, C ^ C ^ alkenylene, branched QC ^ alkenyl, and mixtures of these: alkyethyleneoxy units having the formula: - (A) k - (CH 2) m (OCH 2 CH 2) n Z wherein A is the heterogeneous nitrogen or oxygen atom, preferably A is oxygen, the index k is 0 when the heterogeneous atom is absent, k is equal to 1 when the heterogeneous atom is present, Z is: (i) hydrogen; (I) hydroxyl; (iii) -CO2H; (iv) CH2CO2M; (v) -S03-M +; (vi) -OSO3"M +; (vii) d-C3o alkoxy; (viii) substituted aryl, unsubstituted aryl, or mixtures thereof; (ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; (x) alkylamino, and mixtures thereof: A contains nitrogen or oxygen, m is a water-soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12, preferably Z is hydrogen or C- alkoxy. ? -C30; n is from 1 to 100, preferably from 0 to about 20, most preferably from 2 to about 10; and m is from 1 to 12, preferably from about 1 to about 5; s) carboxylate of the formula: Or consists of: i) CiC ^ alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkeniion and mixtures thereof, ii) C?-C22 alkyl substituted with halogen, C3 alkyl - Branched C22, C2-C22 alkenium, branched dC ^ alkenyl, and mixtures thereof, iii) C3-C22 alkyl substituted with polyhydroxy, iv) C3-C22 glycol, v) C1-C22 alkoxy, vi) C3-C alkoxy 22 branched; vii) substituted aryl, unsubstituted aryl, and mixtures thereof; viii) substituted alkylaryl, unsubstituted alkylaryl, and mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) substituted alkoxy, unsubstituted acyxaryl, or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxy, and mixtures thereof; t) substituted siloxy and siloxy of the formula -OSR19R20R21 wherein each R19, R20 and R2 is independently selected from the group consisting of: (i) C22 alkyl, branched C3-C22 alkyl, C2-C22 alkeniio C3-C22 branched alkenyl, or mixtures thereof; (ii) substituted aryl, unsubstituted aryl, or mixtures thereof; (iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; (iv) alkyethyleneoxy of the formula: - (A) v- (CH2) and (OCH2CH2) Z wherein Z consists of: a) hydrogen; b) C 1 -C 30 alkyl, c) hydroxyl; d) -CO2M; e) -CH2CO2M; f) -SO3"M +; g) -OSO3" M +; h) C C alco alkoxy i) substituted aryl, unsubstituted aryne, or mixtures thereof; j) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; k) alkyleneamino; or mixtures thereof; units A consist of nitrogen or oxygen, M is a water-soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; and mixtures of these.
In accordance with the present invention, the preferred axial R units comprise portions having the formula: wherein Y is a linking portion selected from the group consisting of O, CR25R26, OSR25R26, OSnR25R26 and mixtures thereof; wherein R25 and R26 are hydrogen, C1-C4 alkyl, halogen and mixtures thereof; i is 0 or 1, j is from 1 to 3; K is a ligand selected from the group consisting of: a) linear C?-C 30 alkyl, branched C 3 -C 30 alkyl, linear C 2 -C 30 alkenyl, branched C 3 -C 30 alkenyl, C 6 -C 20 aryl, arylalkyl
C7-C2u > C -C20 alkylaryl and mixtures thereof; b) an alkylethyloxy unit of the formula: - (R23) and (OR22) xOZ wherein Z is selected from the group consisting of hydrogen, C1-C2o alkyl, branched C3-C20 alkyl, linear C2-C2 alkenylene, branched C3-C20 alkenyl, C6-C2o aryl, C7-C3 arylalkio, C6-C20 alkylaryl, and mixtures thereof; R22 is selected from the group consisting of linear C1-C4 alkylene, branched C3-C alkylene, C3-Cß hydroxyalkylene, and mixtures thereof; R23 is selected from the group consisting of C2-C2o alkylene, branched C3-C20 alkylene, C6-C20 arylene. C7-C3U arylalkylene, C7-C3o alkylarylene and mixtures thereof; x is from 1 to 100; and is 0 or 1; and Q is an ionic portion having the formula: -R24-W wherein R24 is selected from the group consisting of linear C3-C3o alkylene, branched C3-C30 alkylene, linear C2-C30 alkenylene, C3-alkenylene Branched C3, arylene of Cß-C-iß and mixtures thereof; W is selected from the group consisting of alkyleneamino -C02"M +, -SO3" M +, -OSO3"M +; PO32" M +, -OPO3"M +; M is a water-soluble cation of sufficient charge to provide electronic neutrality and X is a water-soluble anion as defined hereinabove .. Preferred axial R units are alkylalkylenoxy units of the formula: - (R23) and (OR22) xOZ wherein Z is selected from the group consisting of hydrogen, Linear C7-C20, branched C3-C2o alkyl, linear C2-C20 alkenyl, branched C3-C2o alkenyl, C6-C6 aryl, C7-C2 arylalkyl, C7-C alkylaryl and mixtures thereof R22 is selected from the group consisting of linear C1-C4 alkylene, branched C3-C4 alkylene and mixtures thereof, R23 is selected from the group consisting of C2-C6 alkylene, branched C3-C6 alkylene, arylene of C6-C-? o and mixtures thereof, x is from 1 to 50, and is 0 or 1. The most preferred axial R units comprise and equal to 0, Z is hydrogen, C?-C2o alkyl, branched C3-C20 alkyl, Ce-C ar ar aryl and mixtures thereof, most preferably Z is hydrogen or linear C C-C2 alquilo alkyl, C alquilo-alkyl C20 branched; R22 is linear C1-C4 alkylene, or branched C3-C4 alkylene. R units which are also preferred have the formula: YrQj where Y is a linker portion selected from the group consisting of O, CR25R26, OSiR25R26, OsnR25R26 and mixtures thereof; i is 0 or 1, j is from 1 to 3; Q is an ionic portion having the formula: - R24-W wherein R24 is selected from the group consisting of linear C2-C20 aiquilene, branched C3-C2o alkylene, linear C2-C20 alkenylene, C3-C2 alkenylene branched, C6 ~ arylene and mixtures thereof; W is selected from the group consisting of alkylene amino-CO 2"M +, -SO 3" M +, - OSO 3"M +; PO 32" M +, -OPO 3'M +; M is a water-soluble cation of sufficient charge to provide electronic neutrality and X is a water-soluble anion as defined hereinabove. A hydrophilic unit R that is preferred has the index i equal to 1; R24 is linear C3-C2o alkylene, branched C3-C20 alkylene; P is -CO2"M +, -SO3" M +, -OSO3"M + and M is a water soluble cation of sufficient charge to provide electronic neutrality Examples of Y units suitable for use in units
R have the formula: -Yi-Kj have the formula: - Sn-K1, - OSn-K1 where i is equal to 1 and j equals 1. Additional examples have the formula:
where i is equal to 1 and j equals 3. The above examples also apply to the Y units when used with ionic portions Q. The present invention also relates to laundry detergent compositions comprising: a) at least about 0.1% by weight, preferably from about 0.1% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20% by weight of a detersive surfactant, said Detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic and ampholytic surfactants and mixtures thereof; b) at least about 0.001 ppm, preferably about 0.01 to about 10000 ppm, most preferably about 0.1 to about 5000 ppm, still most preferably about 10 to about 1000 ppm, of a source of superoxide, preferably a superoxide generator of formula:
D D
D R where P is a photosensitizing group; each D is independently a portion capable of promoting singlet oxygen production, as described above; and R is an axial portion that regulates the solubility or substantivity of the superoxide generator described hereinabove; and c) the rest vehicles and auxiliary ingredients. It is also an object of the present invention to provide hard surface cleaning compositions that can be used to clean or disinfect hard surfaces, said compositions comprising: a) at least 0.1%, preferably from about 0.1% to about 30%, very preferably from about 1% to about 30% by weight, most preferably from about 5% to about 20% by weight of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic surfactants , non-ionic, zwitterionic, amphotylic, and mixtures thereof; b) at least about 0.001 ppm, preferably from about 0.01 to about 10000 ppm, most preferably from about 0.1 to about 5000 ppm, still most preferably from about 10 to about 1000 ppm, of a photochemical superoxide disinfectant generator that has the formula:
D D
D R
where P is a photosensitizing group; each D is independently a portion capable of promoting singlet oxygen production; and R is an axial portion that regulates the solubility or substantivity of the superoxide generator described hereinabove; and c) the rest vehicles and auxiliary ingredients, said auxiliary ingredients are chosen from the group consisting of pH regulators, detergency builders, chelating agents, filler salts, soil release agents, dispersants, enzymes, enzyme promoters, perfumes, thickeners, abrasives , solvents, clays, and mixtures of these.
The present invention also relates to a method for cleaning a stained fabric, which consists in contacting a stained cloth that needs to be cleaned with an aqueous cleaning solution consisting of at least 0.001 ppm of a superoxide generator, according to the invention. present invention, followed by exposure of the surface of the treated fabric to a light source having a minimum length of about 300 to about 1200 nanometers.
The present invention also relates to a method for cleaning a hard surface consisting of contacting a hard surface when it is necessary to clean it with an aqueous cleaning composition consisting of at least 0.001 ppm of a superoxide generator, according to the present invention. and exposing the hard surface to a light source having a minimum wavelength range of about 300 to about 1200 nanometers.
The present invention also relates to a method for cleaning a fabric stained with a cleaning material consisting of a low-aqueous cleaning composition consisting of contacting the stained fabric when it is necessary to remove the stain with a cleaning solution of low water content containing less than 50% water and at least 0.001 ppm superoxide generator, according to the present invention, followed by exposure of the surface of the treated fabric to a light source having a wavelength range minimum of about 300 to about 1200 nanometers.
The present invention also relates to a method for cleaning a hard surface with a low water cleaning composition consisting of contacting a hard surface when it is necessary to clean it with a low water cleaning composition consisting of less than 50% water and at least 0.001 ppm of a superoxide generator, according to the present invention and exposing the hard surface to a light source having a minimum wavelength range of about 300 to about 1200 nanometers. Surfactant - The singlet oxygen generator contains compositions comprising from about 0.001% to about 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, amphocytic and zwitterionic surfactants. For liquid systems, the surfactant is preferably present at the scale of about 0.1% to about 20% by weight of the composition. For solid (i.e., granulated) and viscous semi-solid (i.e., gelatinous, paste, etc.) systems, the surfactant is preferably present at the scale of about 1.5% to 30% by weight of the composition. Non-limiting examples of surfactants useful herein typically at levels of about 1% to about 55% by weight, include conventional C ^ -C ^ alkylbenzene sulfonates
("LAS") and C10-C20 primary alkylsulfates of branched and random chain
("AS"), the secondary alkyl sulfates (2,3) of C10-C18 of the formula
CH3 (CH2) x (CHOSO3-M +) CH3 and CH3 (CH2) and (CHOSO3-M +) CH2CH3, where x and (y + 1) are integers of at least about 7, preferably at least 9, and M is a cation which is solubilized in water, especially sodium, unsaturated sulfates such as oleiisulfate, the alkylalkoxysulfates of Cl0"c18 (" AEXS ", especially ethoxysulfates EO 1-7), alkylalkoxycarboxylates of CJ O- -IS (especially the ethoxycarboxylates EO 1) -5), the glycerol ethers of CI QCI S- 'alkyl polyglycosides of C- | o_C- | 8 and their corresponding sulphated polyglucosides, and alphasulfonated fatty acid esters of C- | 2-C-i8- If desired, conventional non-ionic and amphoteric surfactants such as the alkyl ethoxylates of C- | -C «| 8 (" AE ") including the so-called narrow-chain alkylethoxylates and C5-C? 2 alkylphenol-alkoxylates (especially ethoxylated and mixed ethoxy / propoxy) ), betaines and sulfobetaines of C- | 2-C- | 8 ("sultaines"), amine oxides of C? o-i8 > and simila res, can also be included in the global compositions. The N-alkyl polyhydroxylic acid amides of C-J Q-C-J S can also be used. Typical examples include N-methylglucamides of
C-J2-C18- See WO 9,206,154. Other surfactants derived from sugar include the N-alkoxy-polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide of C-jQ-C-jß- The N-propyl to N-hexyl glucamides of C-j2-C -) 8 can be used for low foaming. Conventional C-jrj-C20 soaps can also be used. If high foaming is desired, branched chain CJ Q-CJ Q soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are included in conventional texts.
The anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms, and a radical selected from the group consisting of suifonic acid and sulfuric acid ester radicals (included in the term alkyl, is the alkyl portion of higher acyl radicals). Important examples of the synthetic anionic detergents which can form the surfactant component of the compositions of the present invention are sodium or potassium alkyl sulphates, especially those obtained by sulfating higher alcohols (C8-18 carbon atoms) produced by reducing tallow glycerides or coconut oil; sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms (the alkyl radical can be a straight or branched aliphatic chain); alkyl glyceryl sodium ether sulfonates, especially the ethers of higher alcohols derived from tallow and coconut oil; monoglyceride sulfates and fatty acid sulfonates of sodium coconut oil; Sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of the higher fatty alcohol (eg tallow or coconut alcohols) and from about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of ethylene oxide ether sulfates of alkylphenol having from about 1 to about 10 ethylene oxide units per molecule, and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from sodium or potassium salts of coconut oil of fatty acid amides of a methyl tauride, in which the fatty acids, for example, are derived from coconut oil and beta- sodium or potassium acetoxy or beta-acetamido-alcansulfonates, where the alkane has from 8 to 22 carbon atoms. Additionally, the secondary alkyl sulphates can be used by the formulator exclusively in conjunction with other surfactant materials, and the following identifies and illustrates the differences between the sulfated surfactants and otherwise the conventional alkyl sulfate surfactants. Non-limiting examples of said ingredients are the following. The conventional primary alkyl sulphates, such as those illustrated above, have the general formula ROS03-M +, wherein R is typically a linear C8-22 hydrocarbyl group, and M is a water solubilizing cation. Branched chain primary alkylsulfate surfactants (ie, branched chain "PAS") having from 8 to 20 carbon atoms are also known; see, for example, European Patent Application 439,316, Smith et al., filed January 21, 1991. Conventional secondary alkyl sulfate surfactants are those materials that have the sulfate portion distributed randomly along the "base structure" hydrocarbyl of the molecule. Such materials can be represented by the structure CH3 (CH2) n (CHOSO3-M +) (CH2) mCH3 where m and n are integers of 2 or more, and the sum of m + n is typically from about 9 to about 17, and M it is a cation of solubilization in water. The secondary alkyl sulfates mentioned above are those prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is described in the U.S. patent. No. 3,234,258, Morris, issued February 8, 1996, or in the US patent. No. 5,075,041, Lutz, issued December 24, 1991. The synthesis that is carried out in solvents that produce secondary alkylsulfates (2,3) by cooling, produces products that, when purified to remove materials that did not react , randomly sulfated materials, unsulfated by-products such as C10 and higher alcohols, secondary oleofinsulphonates, and the like, are typically 90 +% pure mixtures of 2- and 3-sulphated materials (some amount of sodium sulfate may be present), and They are white solids, not sticky and apparently crystalline. Some 2,3-disulphates may also be present, but generally comprise not more than 5% of the mixture of secondary alkylammonosulfate (2,3). Such materials are available under the name "DAN", for example, "DAN 200" from Shell Oil Company.
AUXILIARY MATERIALS
The following are non-limiting examples of auxiliary ingredients suitable for use in either laundry or hard surface cleaning or disinfecting compositions in accordance with the present invention. Chelating Agents - The photo-disinfecting compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as defined below. Without intending to be limited by theory, it is thought that certain chelating agents will interact with the photo-disinfectants of the present invention to increase their absorbance in the visible light spectrum. This is a process that is due to the ability of the chelating agents to help effect the "substantivity" of the compounds of the present invention. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraminehexacetates, diethylenetriaminepentacetates and ethanol diglycins, the alkali metal, ammonium and substituted ammonium salts described herein, and mixtures thereof. .
A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer, as described in the U.S.A. 4,704,233, from November 3, 1987, to Hartman and Perkins. If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.1% to about 3.% by weight of said compositions. Inert Salts - The inert salts (filler salts) used in the compositions of the present invention can be any water-soluble organic or inorganic salt, or mixtures of said salts, which do not destabilize the surfactant present. For the purposes of the present invention, "water soluble" means having a solubility in water of at least 1 g per 100 g of water at 20 ° C. Examples of suitable salts include various sulfates, chlorides, borates, bromides, fluorides, phosphates, carbonates, bicarbonates, citrates, acetates, lactates, etc. of alkali metal and / or alkaline earth metal. Specific examples of suitable salts include sodium sulfate, sodium chloride, potassium chloride, sodium carbonate, potassium sulfate, lithium chloride, lithium sulfate, tripotassium phosphate, sodium borate, potassium bromide, potassium fluoride, bicarbonate of sodium, magnesium sulfate, magnesium chloride, sodium citrate, sodium acetate, magnesium lactate, sodium fluoride, etc. Preferred salts are inorganic salts, preferably alkali metal sulfates and chlorides. Particularly preferred salts, due to their low cost, are sodium sulfate and sodium chloride. The salts are present in the compositions at levels from 0% to 40%, preferably from 10% to 20%.
EXAMPLE 1 Preparation of Silica phthalocyanine dichloride
To a mixture of 1,3-diiminoisoindoline (0.333 g, 2.3 mmol) and anhydrous quinoline (15 ml) under a blanket of argon, silicon tetrachloride (1.1 g, 6.5 mmole) is added. The mixture is reduced in an oil bath at 60 ° C for 0.5 hours, heated to reflux for 0.5 hours, stirred at reflux for another 0.5 hour, and cooled for 1 hour. To this solution is added methanol (10 ml), and the resulting mixture is allowed to stand at room temperature for 24 hours. The blue solid formed after standing is filtered, rinsed twice with 10 ml portions of methanol, dried under vacuum at 120 ° C, and used without further purification. The above process is suitable for use in the preparation of silicon naphthalocyanine dichloride using 1,3-diiminobenz- [fj-isoindoline.
EXAMPLE 2 Preparation of phthalo dichloride / silicon naphthalocyanine (VI) 1: 3
To a mixture of 1,3-diiminoisoindoline (0.333 g, 2.3 mmol), 1,3-diiminobenz- [f] -isoindoline (1.35 g, 6.9 mmol) and anhydrous quinoline (15 ml) under a blanket of argon, is added Silicon tetrachloride (2.21 g, 12.9 mmol). The mixture is reduced in an oil bath at 60 ° C for 0.5 hours, heated to reflux for 0.5 hours, stirred at reflux for another 0.5 hour, and cooled for 1 hour. To this solution is added methanol (10 ml), and the resulting mixture is allowed to stand at room temperature for 24 hours. The green solid that is formed is removed by filtration, rinsed twice with 10 ml portions of methanol, dried under vacuum at 120 ° C, and used without further purification.
EXAMPLE 3 Preparation of silicon phthalocyanine dihydroxide
Silica phthalocyanine dichloride (IV) (2 g, 3.3 mmol) is added to a refluxing solution of sodium methoxide (0.8 g, 14.8 mmol) in 95% wet ethanol (15 ml). The reaction mixture is refluxed for 4 hours, and then cooled to room temperature. The resulting product is collected by filtration, rinsed with water and used without further purification.
The above process is suitable for use in the preparation of silicon naphthalocyanine dihydroxide and phthalo dihydroxide / silicon (IV) naphthalocyanine 1: 3.
EXAMPLE 4 Preparation of dilithium naphthalocyanine
To a refluxing solution of 2,3-dicyanonaphthalene (10 g, 56.1 mmol) in anhydrous 1-butanol (330 ml) is added lithium in doses (1.56 g, 224.5 mmol). The solution is refluxed for 6 hours under a blanket of argon, after which the solution is cooled, diluted with absolute methanol (500 ml) and allowed to stand at 0 ° C for 18 hours. The resulting green solid is collected by filtration, dried under vacuum at 80 ° C, and used without further purification. The above process is suitable for use in the preparation of phthalocyanine of 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29, 31-dilithium from 3,6-dibutoxyphthalonitrile; phthalocyanine of 2, 3, 9, 10, 16, 17, 23, 24-octachloro-29-31 -dilithium from 4,5-dichlorophthalonitrile; and tetrabutoxy-29,31 -dilithium phthalocyanine from 3-butoxyphthalonitrile, where there is a mixture of isomers.
EXAMPLE 5 Preparation of naphthalocyanine
To a solution of naphthalocyanine of dilithium (2 g, 2.75 mmol) in N, N-dimethylformamide (200 ml) is added hydrochloric acid at 1 N (10 ml). The solution is stirred at room temperature for 1 hour. Distilled water (200 ml) is added to this solution for approximately 0.5 hours. The resulting green solid is collected by filtration, dried under vacuum at 100 ° C, and used without further purification. The above process is suitable for use in the preparation of 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29H, 31 H-phthaiocyanine; 2, 3, 9, 10, 16, 17, 23, 24-octachloro-29H, 31 H-phthalocyanine; and tetrabutoxy-29H, 31H-phthalocyanine.
EXAMPLE 6
Preparation of phthalocyanine silicon-di- (triethanolamine)
A mixture of silicon phthalocyanine dihydroxide (0.25 gm,
0. 44 mmol), anhydrous trietalonamine (10 gm, 67 mmol) and silenes (175 mL) is heated under reflux for 1.5 hours. The solution is refluxed for 2 hours while the water is removed by azeotropic distillation.
The reaction mixture is cooled and the solvent is removed in vacuo. The resulting crude oil is dissolved in DMF (50 mL) and added to water (800 mL) for 0.5 hour. A blue solid is formed which is collected by filtration, dried under vacuum at 80 ° C and used without further purification. The above process is suitable for use in the preparation of silicon-di- (triethanolamine) naphthalocyanine and silicon 1: 3 phthalo / naphthatacylamine (VI) -di- (triethanolamine). Cleaning compositions provided in accordance with this invention may be in granular, liquid, stick and the like, and are typically formulated to provide a pH during use in the 9 to 11 scale.; however, in the case of non-aqueous or slightly aqueous compositions, the pH scales may vary outside this scale. Various vehicles such as sodium sulfate, water, water-ethanol, BPP, MPP, EPP, PPP, sodium carbonate, and the like, can usually be used to formulate the finished products. The granules can be produced by spray drying or by agglomeration, using known techniques, to provide products in the density scale of 350-950 g / l. Bars can be formulated using conventional extrusion techniques. The compositions may also contain conventional perfumes, bactericides, hydrotropes, and the like. In the case of non-aqueous or low-aqueous compositions, the cleaning compositions can be applied to an article that will be used to deliver the compositions of the present invention to a fabric or a hard surface. Non-limiting examples of compositions according to this invention are the following:
Ingredients% by weight 7 8 9 10
1. Dirt releasing agent in accordance with the patent of E.U.A. do not. 5,415,807, Gosselink et al., Issued May 16, 1995. 2. Photobleaching agent according to example 6.
Claims (21)
1. - A photochemical superoxide generator, characterized in that it has the formula: D 1 D 1 I 1 P or I P 1 1 1 D R wherein P is a photosensitizing group; each D is independently a unit of formula: - L1- E or - L1- B-. { L2- E] m where B is a unit capable of providing a branch point; L1 and L2 are link units; the E units are electron transfer, which have the formula: wherein each W1 and W2 is independently C4-C4 alkylene; G is hydrogen, an electron acceptor group, and mixtures thereof; m is from 2 to 4 included: a) L1, L2 and B alone or in combination do not form continuous series of conjugated bonds extending from the photosensitizing group P to the E portion; and b) the number of chemical bonds of the photosensitizing group P to unit E is not greater than 20; and R is an axial portion that regulates the solubility or substantivity of the superoxide generator.
2. A compound according to claim 1, further characterized in that the photosensitizing group has the formula: or the formula: wherein M is a metal or non-photoactive metal having a valence greater than 3, rings A, B, C and D are aromatic rings, each of said rings are independently selected from the group consisting of benzene, 1, 2- naphthalene, 2,3-naphthalene, anthracene, phenanthrene, and mixtures thereof.
3. The compound according to claim 2, further characterized in that the rings A, B, C and D are each independently: i) a benzene ring unit having the formula: ii) a ring unit of 2; , 3-naphthylene having the formula: iii) a 1,2-naphthylene ring unit having the formula: v) an anthracene ring unit having the formula: v) a phenanthrene ring unit having the formula: wherein each unit R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C 1 -C 22 alkyl. branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; e) Cr C22 alkyl substituted by halogen, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; f) C3-C22 alkyl substituted by polyhydroxyl; g) C1-C22 alkoxy; h) branched alkoxy having the formula: wherein Z is hydrogen, hydroxyl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy > -C02H, -OCH2CO2H, -SO3"M +, -OSO3_M +, -PO32" M, -OPO32"M, or mixtures thereof; M is a cation soluble in water in an amount sufficient to satisfy the charge equilibrium; 0 or 1, each y has independently the value of 0 to 6, each z has independently the value of 0 to 100, i) substituted aryl and unsubstituted aryl, or mixtures thereof, j) substituted alkylaryl and unsubstituted alkylerynyl, or mixtures thereof: k) substituted aryloxy and unsubstituted aryloxy, or mixtures thereof; I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; m) substituted alkylenediaryl and unsubstituted alkylenediaryl, or mixtures thereof n) thioalkyl of CrC22> branched C3-C22 thioalkyl, or mixtures thereof: o) an ester of the formula -CO2R9, wherein R9 is i) Cr C22 alkyl, branched C3-C22 alkyl, alkenyl of C2-C22, branched C3-C22 alkenyl, or mixtures thereof; ii) C1-C alkyl 22 substituted by halogen, branched C3-C22 alkyl; C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; iii) C3-C22 alkylene substituted by polyhydroxy; V) C3-C22 glycol; v) CrC22 alkoxy; vi) branched C3-C22 alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of the formula: wherein R10 and R11 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; R12 is: i) hydrogen; ii) C1-C22 alkyl. branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is chlorine, bromine, iodine or other water-soluble anion, v is 0 or 1, u is from 0 to 22; q) an amino unit of the formula: - NR17R18 wherein R17 and R18 are C? -C22 alkyl, branched C3-C22 alkyl, Q2-C22 alkenyl. C3-C22 branched alkenyl, or mixtures thereof; r) an alkylethyleneoxy unit having the formula: wherein Z is: i) hydrogen, ii) hydroxyl, iii) -C02H, iv) -S03"M +, v) -OSO3" M +, vi) substituted alkoxy) , unsubstituted aryl, or mixtures thereof, viii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; ix) alkyleneamino, or mixtures thereof; A is nitrogen or oxygen; M is a cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12; s) substituted siloxy of the formula -OSR19R20R2 wherein each R19, R20 and R2 is independently: i) C1-C22 alkyl. branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; iv) an alkylethyleneoxy unit of the formula: __ (AX CH2) and (OCH2CH2) ΔZ wherein Z is: a) hydrogen, b) hydroxyl, c) -CO2H, d) -SO3"M +, e) -OSO3" M +, f) C C β alkoxy, g) substituted aryl, unsubstituted aryl, or mixtures thereof, h) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i) alkyleneamino, or mixtures thereof; A is nitrogen or oxygen; M is a cation soluble in water; v is 0 or 1; x is from 0 to 100; and is from 0 to 12, and mixtures thereof.
4. - A compound according to claim 1, further characterized in that G is selected from the group consisting of halogen, nitrogen, cyano, substituted or unsubstituted phenyl, hydroxyl, alkoxy, -CO2R29, - CO2M, -SO3M, -OSO3M, - PO3M, -OPO3M, further characterized in that R29 is an alkyl of CC? 2 alkyneoxy units having the formula: R28 R28 - [0 (CH2)?] [0 (CH2CH)] j [0 (CHCH2)] kZ further characterized in that R28 is a C1-C4 alkyl, Z is hydrogen, C1-C22 alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkylamino, -SO3"M +, -OSO3" M +, -CO2H, and mixtures of this, the index x have the value of 1 to 4, i have the value of 0 to 20, the index j has a value of 0 to 20, the index k has the value 0 to 20, the alkylamino units have the formula: further characterized in that R10 and R1 are each a C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, R12 is hydrogen, C1-C22 alkyl, C3-alkyl Branched C22, C2-C22 alkenyl, C3-C22 alkenyl and mixtures of these, A is the heterogeneous nitrogen or oxygen atom, the index of v is 0 when the heterogeneous atom is absent, v equals 1 when the atom heterogeneous is present, X is chloride bromide, iodide or other water-soluble anion, or is 0 to 22, and mixtures of these.
5. A compound according to claim 4, further characterized in that G is: a) C C-iß alkoxy, b) hydroxyl c) -CO 2 R 29; d) -CO2M; e) -SO3M; f) ethyleneoxy of the formula: - (OCH2CH2) xZ further characterized in that Z is: i) hydrogen; ii) hydroxyl; iii) C-r alkoxy C22 iv) -CO2M; v) -CH2CO2M; vi) -SO3M; vii) -OSO3M; viii) alkyleneamino; and mixtures thereof, M is hydrogen, a cation soluble in water, x is from 1 to 20.
6. A compound according to claim 1, further characterized in that L1 and L2 are independently selected from the group consisting of oxygen, linear or branched C1-C-18 alkylene, linear or branched C1-C18 alkenylene; linear or branched C1-C-18 alkyleneoxy, substituted or unsubstituted C1-C18 arylene, substituted or unsubstituted C-1-C18 alkyleneanl, substituted or unsubstituted or unsubstituted C C-is aryleneoxy, CiC oxyalkylenenariene -iβ substituted or unsubstituted, substituted or unsubstituted CiC-iβ alkylenenoxylen, and mixtures thereof.
7. A compound according to claim 1, further characterized in that the branched unit has the formula: I B B B ^ further characterized in that B is an atom capable of forming 3 to 5 covalent bonds to linking units L1 and L2, where B is selected from the group consisting of boron, aluminum, nitrogen, phosphorus, carbon, silicon, tin, germanium and mixtures of these, preferably carbon.
8. A compound according to claim 1, further characterized in that the units R are axial units and where each unit R independently is chosen from the group consisting of: a) hydrogen; b) allogeneic; c) hydroxyl; d) cyano; e) C1-C22 alkyl, branched C4-C22 alkyl, C2-C22 alkenium, branched C4-C22 alkenyl, or mixtures thereof; f) C 1 -C 22 alkyl substituted with halogen, C 2 -C 2 alkyl branched C 2 -C 22 alkenyl, branched C 4 -C 22 alkenyl, or mixtures thereof; g) C3-C2 alkyl substituted with polyhydroxyl; h) Ci-C ^ alkoxy; i) branched alkoxy of the formula: (0) x (CH2) and (OCH2CH2) z Z (O) x (CH2) and (OCH2CH2) z Z Z further characterized in that Z is hydrogen, hydroxyl, C 1 -C 30 alkyl, C 1 -C 30 akoxy. -CO2H, -CH2CO2H, -SO3-M +, -OSO3"M +, -PO32 M, -OPO32" M, and mixtures thereof; M is a cation soluble in water in sufficient quantity to satisfy the charge equilibrium; x is 0 or 1, each and independently has the value of 0 to 6, each z independently have the value of 0 to 100; j) substituted aryl, unsubstituted aryl, or mixtures thereof; k) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; I) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; m) substituted oxyalkylenearyl, oxyalkylenearyl, or mixtures thereof; n) substituted alkyleneoxyaryl, alkyleneoxyaryl, or mixtures thereof; o) C1-C22 thioalkyl, branched C4-C22 thioalkyl or mixtures thereof; p) an alkyleneamino unit of the formula: wherein R10 and R11 consists of a C1-C22 alkyl, branched C4-C22 alkyl, C2-C22 alkenyl, branched C4-C22 alkenyl, or mixtures thereof; R12 consists of i) hydrogen; I) C1-C22 alkyl, branched C4-C22 alkyl, C2-C22 alkenyl, branched C4-C22 alkenyl, or mixtures thereof; units A consist of nitrogen or oxygen; X consists of chloride, bromide, iodide, or other water-soluble anion, v is 0 or 1, u is from 0 to 22; q) an amino unit of the formula: -NR17R18 wherein R17 and R18 consist of a C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkeniio, branched C3-C22 alkenyl, and mixtures thereof; r) an alkylethyleneoxy unit of the formula: - (A) v- (CH2) and (OCH2CH2) Z where Z consists of: i) hydrogen; ii) hydroxyl; iii) -CO2H; V) -CH2CO2M; v) - SO3"m +; vi) -OSO3" M +; vii) C1-C30 alkoxy; viii) substituted aryl, unsubstituted aryl, or mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) alkyienamino; and mixtures of these; A consists of nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; s) carboxylate of the formula: O - O-C- R9 wherein R 9 consists of: i) C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl and mixtures thereof; ii) C1-C22 alkyl substituted with allogen, branched C3-C22 alkyl, C2-C22 alkenniium, branched C3-C22 alkenyl and mixtures thereof; Ii) C3-C22 alkyl substituted with polydroxyl; iv) C3-C22 licol; v) C1-C22 akoxy; vi) branched C 4 -C 22 alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted alkylaryl, unsubstituted alkylaryl, or mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) substituted alkoxyaryl, unsubstituted alkoxyaryl, or mixtures thereof; xi) unsubstituted alkyleneoxyaryl substituted alkylenenoxyaryl, or mixtures thereof; t) substituted siloxy of the formula: -OSiR19R20R21 wherein each R19, R20, and R21 are independently selected from the group consisting of: i) C1-C22 alkyl, branched C3-C2 alkyl, C2-C22 alkenyl, alkenyl of branched C3-C22 or mixtures of these; ii) substituted aryl, unsubstituted aryl, or mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; iv) an alkylethyleneoxy unit of the formula: - (AV- (CH2) and (OCH2CH2) xZ; wherein Z consists of: a) hydrogen; b) C 1 -C 30 alkyl, c) hydroxyl; d) -CO2M; e) -CH2CO2M; f) -SO3"M +;) -OSO3" M +; h) CrC6 alkoxy) i) substituted aryl, unsubstituted aryl or mixtures thereof; j) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; k) alkyleneamino; or mixtures thereof; units A consist of nitrogen or oxygen, M is a water soluble cation, v is 0 or 1 x is from 0 to 100, and is from 0 to 12; and mixtures of these.
9. A compound according to claim 8, further characterized in that the axial R units have the formula: wherein Y is a linkage portion selected from the group consisting of O, CR25R26, OSiR25R26, OSnR25R26, and mixtures thereof, in wherein R25 and R26 are hydrogen, C1-C2 alkyl halogen, and mixtures thereof; i is 0 or 1, j is from 1 to 3; K is a ligand selected from the group consisting of: a) linear C?-C 30 alkyl, branched C 3 -C 30 alkyl, linear C 2 -C 30 alkenyl, branched C 3 -C 30 alkenyl, C 6 -C 20 aryl, aryalkyl C -C2o, C7-C2o alkyaryl; b) an alkylethyleneoxy unit of the formula: - (R23) and (OR22) xOZ wherein Z is hydrogen, C7-C20 alkyl, branched C3-C2o alkyl, linear C2-C2 alkenylene, branched C3-C2 alkenyl , C6-C20 aryio, C7-C3 arylalkyl, C6-C2o alkylaryl; R22 is linear C1-C4 alkylene, branched C1-C4 alkylene, C3-C6 hydroxyalkylene, and mixtures thereof; R23 is selected from the group consisting of C2-C20 alkylene, branched C3-C20 alkylene, C6-C2 arylene, C-C30 aryalkylene, C7-C30 alkylarylene; x is from 1 to 100; and is 0 or 1; and c) mixtures thereof; Q is an ionic portion having the formula: -R24-W wherein R24 is selected from the group consisting of linear C3-C3u alkylene, branched C3-C3o alkylene, alkenylene C2-C30 linear alkenylene C3-C3o branched , Cß-Ci? arylene and mixtures thereof; W is selected from the group consisting of -CO2-M +, -SO3"M +, -OSO3" M +; PO32-M +, -OPO3"M +, alkyleneamino, M is a water-soluble cation of sufficient charge to provide electrical neutrality and X is a water-soluble anion
10. A laundry detergent composition consisting of: a) less about 0.1%, preferably from about 0.1% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20% by weight, of a surfactant detersive, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic, and mixtures thereof, b) at least about 0.001 ppm, preferably about 0.01 to about 10000 ppm, most preferably from about 0.1 to about 5000 ppm, still most preferably from about 10 to about 1000 ppm, of a strong superoxide, and c) remaining vehicles and auxiliary ingredients.
11. - A composition according to claim 10, further characterized in that the source of superoxide is a photochemical superoxide generator having the formula: D D D R where P is a photosensitizing group that has the formula: or that has the formula: wherein M is a non-metal photoactive metal having a valence greater than 3, rings A, B, C, and D are aromatic rings, each of said rings independently being selected from the group consisting of benzene, 1, 2- naphthalens, 2, 3-naphthalene, anthracene, phenanthrene, and mixtures thereof; each D is independently a unit that has the formula: -L1- -L1-B- [L2-E], m where B is a branch point unit capable of providing 3 to 5 covalent bonds to units L1 and L2 that have the formula: where B is selected from the group consisting of boron, aluminum, nitrogen, phosphorus, carbon, silicon, tin, germanium and mixtures thereof, preferably carbon; L1 and L2 are linking units independently selected from the group consisting of oxygen, linear or branched C-i-C-is alkylene, linear or branched C C al 8 alkylene; linear or branched Ci-ds alkenyloxy, substituted or unsubstituted C1-C18 aryiene, substituted or unsubstituted C-? -C-18 alkylenearylene, substituted or unsubstituted C? -C-? 8 aryleneoxy, C1-oxyalkylenearylene -C 18, substituted or unsubstituted, substituted or unsubstituted C 1 -C 8 alkylene oxide, and mixtures thereof; the units E are electron transfer units having the formula: wherein each W1 and W2 is independently alkylene C -? - C4; G is hydrogen, an electron acceptor group, and mixtures thereof; m is from 2 to 4; since: a) L1, L2 and B alone or in combination do not form a continuous series of conjugated bonds extending from the photosensitizing group P to the E portion; and b) the number of chemical bonds of the photosensitizing group P to unit E are not greater than 20; and R is an axial portion that regulates the solubility or substantivity of the superoxide generator.
12. A composition according to claim 11, further characterized in that the rings A, B, C, and D are each independently: i) a benzene ring unit having the formula: I) a 2,3-naphthylene ring unit having the formula: iii) a 1, 2-naphthylene ring unit having the formula; iv) an anthracene ring unit having the formula: v) a phenanthrene ring unit having the formula: wherein each unit R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from the group consisting of: a) hydrogen, b) halogen, c) hydroxyl, d) C? -C22 alkyl, alkyl of branched C3-C22, C2-C22 alkenyl. C3-C22 branched alkenyl or mixtures thereof; e) C 1 -C 22 alkyl substituted with halogen, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof; f) C3-C22 alkyl substituted with polyhydroxyl; g) CrC22 alkoxy, h) branched alkoxy having the formula: (0) x (CH2) and (OCH2CH2) z Z (0)? (CH2) and (OCH2CH2) z Z wherein Z is hydrogen, hydroxyl, C -? - C3o alkyl, C- | -C30 alkoxy, d-Cao alkoxy, -CO2H, .OCH2CO2H, -S03"M +, -OSO3'M +, -PO32'M , -OPO32"M, or mixtures thereof, M is a cation soluble in water in an amount sufficient to satisfy the charge equilibrium; x is 0 or 1, each independent has the value of 0 to 6, each z independently has the value of 0 to 100; i) substituted aryl, unsubstituted aryl or mixtures thereof; j) substituted alkylenearyl, unsubstituted alkylaryl, or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl or mixtures thereof, n) C1-C22 thioalkyl, branched C3-C22 thioalkyl or mixtures thereof; or an ether of the form -CO 2 R 9 wherein R 9 is i) C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof; ii) C1-C22 alkyl substid with halogen, branched C3-C22 alkyl, C2-C22 alkenyl. C2-C22 alkenyl. C3-C22 branched alkenyl, or mixtures thereof, iii) C3-C22 alkylene substid with polyhydroxyl, iv) C3-C22 glycol; v) C3-C22 alkoxy, vi) branched C3-C22 alkoxy, vii) substid aryl, unsubstid ary as mixtures thereof; viii) substid alkylenearyl, unsubstid alkylenearyl or mixtures thereof; ix) substid aryloxy, unsubstid aryloxy or mixtures thereof; x) substid oxyalkylenearyl, unsubstid oxyalkylearyl or mixtures thereof; xi) substid alkyleneoxyaryl, unsubstid alkyleneoxyaryl or mixtures thereof; p) an alkyleneamino unit of the formula. wherein R10 and R11 are C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; R12 is: i) hydrogen; ii) C?-C22 alkyl > branched C3-C22 alkyl, C2-C22 alkenyl. alkenyl, C3-C22 branched, or mixtures thereof; A is nitrogen or oxygen; X is chloride, bromide, iodide or other water-soluble anion, v is 0 or 1, u is from 0 to 22; q) an amino unit of the formula: - NR17R18 wherein R? 7 and R? 8 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; R is an alkylethyleneoxy unit of the formula: - (A) v- (CH 2) y (OCH 2 CH 2) x Z wherein Z is: i) hydrogen; ii) hydroxyl; iii) -CO2H; V) -SO 3"M +; v) -OSO 3'M +; vi) C C β alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; ix) alkyleneamino, or mixtures thereof: A is nitrogen or oxygen, M is a water-soluble cation, v is 0 or 1, x is from 0 to 100, and is 0 to 12; s) substituted siloxy of the formula : -OSiR19R20R21 wherein each R19, R20 and R21 is independently i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; ii) substituted aryl; unsubstituted aryl, or mixtures thereof, iii) substituted aryioxy, unsubstituted aryioxy or mixtures thereof, iv) an alkylethylaxy unit of the formula: - (A) v- <CH2) and (OCH2CH2) xZ; Z is: (a) hydrogen, b) hydroxyl, c) -CO2H, d) -S03-M +, e) -OSO3"M +; f) C 1 -C 2 alkoxy; g) substituted aryl, unsubstituted aryl, or mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; i) alkyleneamino, or mixtures thereof; A is nitrogen or oxygen, M is a water-soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; and mixtures of these.
13. A composition according to claim 11, wherein G is selected from the group consisting of halogen, nitrogen, cyano, substituted or unsubstituted phenyl, hydroxyl, alkoxy, -CO2R29, -CO2M, -SO3M, - OSO3M, -PO3M , -OPO3M, wherein R29 is C? -C12 alkyl, alkyleneoxy units having the formula: wherein R28 is C1-C4 alkyl; Z is hydrogen, C1-C22 alkoxy, aryl, substituted aryl, aryioxy, substituted aryloxy, alkyleneamino, -SO3"M +, -OSO3" M +, -CO2H, and mixtures thereof, the index x has the value of 1 to 4; i has the value from 0 to 20, the index j has the value from 0 to 20, the index k has the value from 0 to 20; the alkyleneamino units have the formula: wherein R 10 and R 11 each are a C 1 -C 22 alkyl, a branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, R 2 is hydrogen, C 1 -C 22 alkyl, C 3 alkyl Branched -C23, C2-C22 alkenyl, C2-C22 alkenyl, branched C3-C22 alkenyl and mixtures thereof, A is the heterogeneous nitrogen or oxygen atom, the index v is 0 when the heterogeneous atom is absent, v is equal to 1 when the heterogeneous atom is present, X is chloride, bromide, iodide, or other water soluble anion, or is from 0 to 22, and mixtures thereof.
14. - A composition according to claim 13, further characterized in that G is: a) C 1 -C 16 alkoxy; b) hydroxyl; c > - d) -CO2M; e) -SO3M; f) ethyleneoxy of the formula: - (OCH 2 CH 2) x Z wherein Z is: i) hydrogen; ii) hydroxyl; iii) C? -C22 alkoxy; V) -CO2M; v) - CH2CO2M vi) -S03M; vii) -OSO3M; or viii) alkyleneamino; and mixtures of these; M is hydrogen, a cation soluble in water; x is from 1 to 20.
15. A composition according to claim 11, further characterized in that the units R are axial units and wherein the unit R is independently chosen from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) C1-C22 alkyl. alkyl of Branched C4-C22, C2-C22 alkenyl, branched C4-C22 alkenyl or mixtures thereof; f) C 1 -C 22 alkyl substituted with halogen, branched C 4 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 4 -C 22 alkenyl, or mixtures thereof; g) C3-C22 alkyl substituted with polyhydroxy; h) C1-C22 alkoxy; and i) branched alkoxy having the formula: Z wherein Z is hydrogen, hydroxyl, CC ^ alkyl, C -? - C30 alkoxy, -CO2H, -CH2CO2H, -XO3"M +, -OSO3" M +, -PO32"M, and mixtures thereof; M is a cation soluble in water in sufficient quantity to satisfy the charge equilibrium, x is 0 or 1, each and independently has the value of 0 to 6, each z independently has the value of 0 to 100, j) substituted aryl, unsubstituted aryl or mixtures thereof: k) substituted alkylenearyl, unsubstituted alkylenearyl or mixtures thereof: I) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof, m) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; n) alkylenediaryl substituted, unsubstituted alkyleneoxyaryl, or mixtures thereof: o) C1-C22 thioalkyl, branched C4-C22 thioalkyl, or mixtures thereof, p) an alkyleneamino unit of the formula: wherein R 10 and R 11 consist of a C 1 -C 22 alkyl, branched C 4 -C 22 alkyl, C 2 -C 22 alkenyl. C4-C22 branched alkenyl, or mixtures thereof; R12 consists of: i) hydrogen; I) C1-C22 alkyl, branched C4-C22 alkyl, C2-C22 alkenyl, branched C4-C22 alkenyl, or mixtures thereof; Units A consist of nitrogen or oxygen; X consists of chloride, bromide, iodide, or other water-soluble anion, v is 0 or 1, u is from 0 to 22; q) an amino unit of the formula: - NR17R18 wherein R17 and R18 consist of a C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, and mixtures thereof; r) an alkylethyleneoxy unit of the formula; __ A) v- (CH2) and (OCH2CH2) Z Z wherein Z consists of: i) hydrogen; ii) hydroxy; iii) -C02H; iv) -CH2CO2M; v) -SO3"M +; vi) -OSO3" M +; vii) C1-C30 alkoxy; viii) substituted aryl, unsubstituted aryl, or mixtures thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) alkyleneamino; and mixtures of these; A consists of nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; s) carboxylate of the formula: wherein R9 consists of: i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, and mixtures thereof; ii) C1-C22 alkyl substituted with halogen, branched C3-C22 alkyl, C3-C22 alkenyl, branched C3-C22 alkenyl, and mixtures thereof; iii) C3-C22 alkyl substituted with polyhydroxyl; iv) C3-C22 glycol; v) C1-C22 alkoxy; vi) branched C 4 -C 22 alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted alkylaryl, unsubstituted alkylaryl, or mixtures thereof; X) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) substituted alkoxyaryl, unsubstituted alkoxyaryl, or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; t) Substituted siloxy of the formula: -OSR19R20R21 wherein each R19, R20 and R21 are independently selected from the group consisting of: i) C?-C22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl C3-C22 branched alkenyl, or mixtures thereof; I) substituted aryl, unsubstituted aryl, or mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; iv) an alkylethyleneoxy unit of the formula: < AV- (CH2) y) OCH2CH2) xZ; wherein Z consists of: a) hydrogen; b) C 1 -C 3 alkyl; c) hydroxyl; d) -CO2M; e) -CH2CO2M; f) -SO3"M +; g) -OSO3" M +; h) C? -C6 alkoxy; i) substituted aryl, non-substituted ary, or mixtures thereof; j) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; k) alkyleneamino; or mixtures thereof; units A consist of nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; and mixtures of these.
16. A composition according to claim 15, further characterized in that the axial R units have the formula: -Yi-Kj or -Yi-Qj wherein Y is a linkage portion chosen from the group consisting of O, CR25R26, OSiR25R26, OSnR25R26, and mixtures of these; wherein R 25 R 26 are hydrogen, C 1 -C 4 alkyl, halogen, mixtures thereof; i is 0 or 1, j is from 1 to 3; K is a ligselected from the group consisting of: a) linear C1-C30 alkyl, branched C3-C3o alkyl, linear C2-C30 alkenyl, branched C3-C3o alkenyl, C6-C2o aryl, C7 arylalkyl -C2o, C7-C2o alkylaryl; b) an alkylethyleneoxy unit of the formula: -. { R23) (OR22) xOZ wherein Z is hydrogen, C7-C2o alkyl, branched C3-C2o alkyl, linear C2-C2o alkenyl, branched C3-C2o alkenyl, C6-C20 aryl. C7-C30 arylalkyl, C6-C2alkylaryl, R22 is linear C-1-C4 alkylene, branched C1-C4 alkylene, C3-C6 hydroxyalkylene, mixtures thereof; R23 is selected from the group consisting of C2-C20 alkylene, branched C3-C20 alkylene, C6-C2 arylene, C3-C3 arylalkylene, C7-C30 alkylarylene; x 10 is from 1 to 100, is 0 or 1; mixtures of these; Q is an ionic portion having the formula: - R24n / v wherein R24 is selected from the group consisting of linear C3-C20 alkylene, branched C3-C3alkylene, linear C2-C3o alkenylene, 15 C3-C30 branched, C6-C16 arylene, and mixture thereof; w is selected from the group consisting of -CO2"M +, -SO3" M +, -OSO3"M +; PO32" M +, -OPO3'M +, alkyleneamino; M is a water-soluble cation of sufficient charge to provide electronic neutrality and X is a water-soluble anion.
17.- A hard surface cleaning composition that consists of 20 of: a) at least about 0.1%, preferably about 0.1% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20% in Weight, of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) at least about 0.001 ppm, preferably from about 0.01 to about 10000 ppm, most preferably from about 0.1 to about 5000 ppm, still very much 5 preferably from about 10 to about 1000 ppm, of a photochemical superoxide disinfectant generator in accordance with the claim 1; and c) the remaining vehicles and auxiliary materials, said auxiliary ingredients are chosen from the group consisting of pH regulators, detergency builders, chelating agents, filling salts, release agents, 10 dirt, dispersants, enzymes, enzyme promoters, perfumes, thickeners, abrasives, solvents, clays, and mixtures thereof.
18.- A method for cleaning a stained cloth that consists of contacting a dirty cloth when it is necessary to clean it with an aqueous cleaning solution consisting of at least 0.001 ppm of the generator. 15 superoxide according to claim 1, followed by exposure of the surface of the treated fabric to a light source having a minimum wavelength range of about 300 to about 1200 nanometers.
19.- A method to clean a hard surface that consists of contacting a hard surface when it is necessary to clean it with a The aqueous cleaning composition consisting of at least 0.001 ppm of the superoxide generator according to claim 1, and of exposing the hard surface to a light source having a minimum wavelength range of about 300 to about of 1200 nanometers.
20. - A method for cleaning a fabric stained with a cleaning material consisting of a low water cleaning composition consisting of contacting a stained fabric when it is necessary to remove the stain with a low water cleaning solution consisting of 5 less than 50% water and at least 0.001 ppm of the superoxide generator according to claim 1, followed by exposure of the surface of the treated fabric to a light source having a minimum wavelength range of about 300 to about 1200 nanometers.
21. A method for cleaning a hard surface with a low water cleaning composition consisting of contacting the hard surface when it is necessary to clean it with a low water cleaning composition consisting of less than 50% water and at least 0.001 ppm of the superoxide generator according to claim 1, and exposing the hard surface to a light source having a minimum wavelength range of about 300 to about 1200 nanometers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/034158 | 1997-01-24 | ||
| US034158 | 1997-01-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99006945A true MXPA99006945A (en) | 2000-01-01 |
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