MXPA99006940A

MXPA99006940A - Low hue photobleaches

Info

Publication number: MXPA99006940A
Application number: MXPA/A/1999/006940A
Authority: MX
Inventors: David Willey Alan
Original assignee: The Procter & Gamble Company; David Willey Alan
Priority date: 1997-01-24
Filing date: 1999-07-26
Publication date: 2000-01-01

Abstract

Low hue photobleaching compositions comprising organotin (IV), organogermanium (IV), organoplatinum (IV), organopalladium (IV), organolead (IV) or organophosphorous (III) phthalocyanine and naphthalocyanines having Q-band absorption maxima at wavelengths greater than 660 nm and increased triplet state yields whereby production of singlet oxygen is increased. Use of Sn4+, Ge4+, Pt4+, Pd4+, Pb4+, P3+ phthalocyanine and naphthalocyanines compounds in photobleaching compositions allows for formulation of low hue laundry compositions, bleach compositions, and hard surface cleaners.

Description

PHOTOBLANKERS OF MATIZ BAJO FIELD OF THE INVENTION The present invention relates to novel photosensitizing compounds of organotin, organogermanium, organoplatinum, organopalladium, organoplomo or organophosphorus having a maximum wavelength of Q-band absorption of 660 nanometers or greater and the use of these as photoactivators (photosensitizers) or producers. of oxygen in singlet, in particular for the photobleaching of low hue to eliminate stains in textiles and hard surfaces. The present invention also relates to laundry compositions and hard surface cleaners consisting of novel photosensitizer compounds of organotin, organogermanium, organoplatinum, organopalladium, organoplomo, or organophosphorus of the present invention. The present invention also relates to a method of assortment of compositions consisting of low-hue photobleaches for stained fabrics and for hard surfaces. BACKGROUND OF THE INVENTION It is known that certain phthalocyanine, naphthalocyanine, and metallocyanine compounds soluble in water can be used as photobleaching and antimicrobial agents. Phthalocyanines, naphthalocyanines, can form "oxygen in singlet "an oxidizing species capable of reacting with bleaching spots to a colorless state and normally soluble in water." There are many examples of phthalocyanine and naphthalocyanine photobleaching agents, the most common being zinc and aluminum phthalocyanines. the term "photosensitizer" instead of "photoactivator" and can therefore be considered as equally suitable for the latter term used throughout this description.The prior art teaches phthalocyanine and naphthalocyanine compounds having the general structure where Me is a transition or non-transition metal, (Sens) is a ring of phthalocyanine or naphthalocyanine which, when combined with a suitable Me unit, is capable of undergoing photosensitization of oxygen molecules, R units are groups substituents that are attached to the photosensitizing ring units (Sens.) to increase the solubility or photochemical properties of the molecule, and the Y units are substituents associated with the metal atom, for example, anions to provide electronic neutrality. The selection of a particular substituent R unit for substitution in the molecule has been the point of interest for many years of research and, typically, the formulator chooses these units to give the target molecule the desired level of water solubility. A major limitation for the use of phthalocyanine and naphthalocyanine compounds for photobleaching fabrics is the fact that these molecules are matte with a high level of coloration. A second limitation is that the compounds are not inherently water soluble. Therefore, it has been the task of the phthalocyanine and naphthalocyanine photobleaners formulators to provide water-soluble photobleaches without adversely affecting their photochemical properties. Another task for photobleaching formulators has been the need to modify the properties of the photosensitizing unit (Sens.) Of the molecule, in other words, increase the quantum efficiency without reducing the solubility in water. By balancing water solubility and improving photophysical properties, the formulator must ensure that structural modifications do not increase color. It is well known to formulators skilled in the art that a unit R that can produce a desired increase in one of these three properties can cause an equally important decrease in one or both of the other desirable properties. Surprisingly, it has been found that the compounds of the present invention allow formulators to modify the levels of solubility, photoeffectivity, maximum Q-band length separately without adversely affecting the other parameters of the molecule. This ability to selectively delineate and modify the key structural elements contributing to the molecule's objective properties allows the formulator to act without having to rely on a random stratagem. The photobleaches of the invention consist of two "elements". The photosensitizer ring that is optimized for color (hue) and oxygen generation in singlet, and axial groups that are optimized to provide the desired level of solubility, substantivity, and separation. These two elements will be described in more detail later in this document. A key to this ability to control the molecular properties is found by contrasting the structure of known photobleaches consisting of phthalocyanines and naphthalocyanines with those of the present invention. The examples of photobleaches described in the prior art are generally planar molecules due to the planar ring structure. This flat character produces a propensity for those molecules to aggregate where this aggregation tends to lead to photochemical extinction, avoiding an efficient singlet oxygen formation. The photosensitizer compounds of organotin, organogermanium, organoplatinum, organopalladium, organoplome or organophosphorus of the present invention consist of axial substituents to break this order effect, thus providing an efficiently formed monolayer of photosensitizers uniformly applied to a given substrate. Because each molecule of this monolayer can now contribute to the bleaching being present, it has a better cost of efficiency for the formulator. It has been surprising to find that due to the separation of physical properties in "molecular sectors", for example R groups for solubility, new uses have been discovered for the compounds of the present invention. Adducts that provide profiles of unique solubility, but that diminish photophysical properties, were once excluded from use in photobleaching agents. However, the inclusion of these portions is the photobleaching of the present invention results in the ability to formulate photobleaches for use in non-common applications, for example dry-cleaning applications. The low aqueous or solvent-based solutions of the present invention can now be obtained for the simple reason that the present invention provides control over the solubility that is manifested in the choice of axial R substitutions. The proper selection of axial R units linked to the compounds of the present invention allows the formulator to balance the photoefficiency changes of the desired compound with the water solubility of the source material. In addition, these modifications of axial R unit give the formulator the ability to balance the solubility, the band Q? Max, and quantum efficiency of the unit (Sens.). It is an object of the present invention to provide "substantive" and "non-substantive" photosensitizers of organotin, organogermanium, organoplatin, organopaladium, organoplomo or organophosphorus.

A "substantive" photosensitizer of organotin, organogermanium, organoplatin, organopalladium, organoplomo or organophosphorus will be attracted to a surface, and a "non-substantive" photosensitizer of organotin, organogermanium, organoplatin, organopalladium, organoply or organophosphorus will repel a surface. Another objective of the present invention is to provide substantive and non-substantive photobleaching laundry compositions for natural, synthetic or mixed fabrics. Another objective of the present invention is to provide photobleaching compositions consisting of non-aqueous carriers and those of low water content, that is, photobleaching compositions having carriers where the water constitutes less than half of the carrier liquid. Another objective of the present invention is to provide hard surface cleaning compositions of substantive and non-substantive photobleaching for hard non-porous surfaces between them, Formica®, ceramic mosaic, glass, or for hard porous surfaces such as concrete or wood. It is an object of the present invention to provide a method for bleaching fabrics with laundry compositions consisting of organotin, organogermanium, organoplatinum, organopalladium, organolead or organophosphor photoblanking compounds of the present invention.

An object of the present invention is to provide a method for cleaning hard surfaces with compositions consisting of organotin, organogermanium, organoplatinum, organopalladium, organolead or organophosphor photobleach compounds of the present invention. It is an object of the present invention to provide the photosensitizing compounds of organotin, organogermanium, organoplatinum, organopalladium, organoplome or organophosphorus having a low wavelength of maximum absorption of Q band of at least 660 nanometers.

TECHNICAL BACKGROUND Various patent documents relate to photochemical bleaching or the use of the phthalocyanine and naphthalocyanine compounds as well as their formulations and synthesis. See, for example, US patent. No. 3,094,536, issued June 18, 1963; US patent A. No. 3,927,967, issued December 23, 1975, patent of E.U.A. No. 4,033,718, issued July 5, 1977; patent of E.U.A. No. 4,166,718, issued September 4, 1979; patent of E.U.A. No. 4,240,920, issued December 23, 1980; patent of E.U.A. No. 4,255,273, issued March 10, 1981; patent of E.U.A. No. 4,256,597, issued March 17, 1981; patent of E.U.A. No. 4,318,883, issued March 9, 1982; patent of E.U.A. No. 4,368,053, issued on January 11, 1983; patent of E.U.A. No. 4,497,741 issued February 5, 1985; patent of E.U.A. No. 4,648,992, issued March 10, 1987 and sun. from pat. of R.U. 1, 372,035, published October 30, 1974; Sun. from pat. of R.U. 1, 408,144, published October 1, 1975; Sun. from pat. of R.U. 2,159,516, published December 4, 1985; E.P. 484,027 A1 published on May 6, 1992; WO 91/18006 published November 28, 1991 and Japanese Kokai 06-73397 Derwent Abst. No. (94-128933) published March 15, 1994. In addition to the patent publications mentioned above, other references describing the synthesis, preparation and properties of phthalocyanines and naphthalocyanines are also incorporated herein by reference; Phthalocyanines: Properties and Applications, Leznoff, C.C. and Lever A.B.P. (Eds), VCH, 1989; Infrared Absorbing Dyes, Matsuoka, M. (Ed), Plenum, 1990; Inorg. Chem., Lowery, M. J. et al., 4 pg 128, (1965); Inorg. Chem. Joyner R.D. and others, 1, pg 236, (1962); Inorg. Chem., Kroenke, W.E. and others 3,696, 1964; Inorg. Chem. Esposito, J.N. and others., 5, pg. 1979, (1966); J.Am. Chem. Soc. Wheeler, B.L. and others., 106 pg. 7404, (1984), lnorg. Chem. Ford, W.E. and others., 31, pg. 3371, (1992); Material Science, Witkiewicz, Z et al., 11, pg. 39, (1978); J. Chem. Soc. Perkin Trans. I, Cook, M.J. and others, pg. 2453, (1988); Acc. Chem. Res., Sayer, P., Gouterman, M., and Connell, C.R., 15, 73-79, (1982); J. Am. Chem. Soc, Snow, A.W. and Jarvis, N. Lynn, 106, 4706-4711, (1986); J. Am. Chem. Soa, Richter, B.D., Kenney, M.E., Ford, W.E. Rodgers, M.A.J., 112, 8064-8070, (1990); Cancer Letters, Soncin M., Polo, L., Reddi, E., Jori, G., Kenny, M.E., Chang, G., and Rodgers, M.A.J., 89, 101-106, (1995); J. Inorg. Nucí Chem., Rafaeloff, R., Kohl, F.J., Krueger, P.C., Kenney, M.E., 28, 899-902, (1966); J. Am. Chem. Soc, Dirk, C.W., Inabe, T., Schoch, Jr., K.F., and Marks, T.J., 105, 1539-1550, (1985); Polyhedron, Nyaokong, T., 2067-71, (1994); Angew. Chem., Int. Ed. Engl., Kato, S., Noda, I., Mizuta, M.M., and Itoh, Y., 18, 82-3, (1979); Photochemistry and Photobiology, Chan, W.-S., Marshall, J.F., Svensen, R., Phillips, D., and Hart, I.R., 45, 757-61, (1987); Inorganic Chemica Acta, Kraut, B., and Ferrandi, G., 149, 273-77, (1988); Inorg. Chem., Kroenke, W.J., and Kenney, M.E., 3, 251-4, (1964).

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to an oxygen generator in photochemical singlet having a maximum wavelength of absorption of Q band of 660 nanometers or greater, having the formula: or the formula: where M is a metal or non-photoactive metal, said metal or non-metal chosen from the group consisting of Sn, Ge, Pt, Pd, Pb, P and mixtures thereof; The units R1, R2, R3, R4, R5 and R6 each are independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; 20 d) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof e) C1-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, C3_3alkyl, C3_3alkoxy, -CO2H, -OCH2CO2H, -SO3'M +, -OS03"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 has independently the value from 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 alkylenearyl or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl or mixtures thereof; m) substituted alkyoxyaryl and unsubstituted alkyleneoxy, or mixtures thereof; n) C1-C22 thioalkium, branched C3-C22 thioalkyl, 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 alkenyl, or mixtures thereof; iii) C3. C22 alkylene substituted by polyhydroxyl, iv) C3-C22 glycol; v) C 1 -C 22 alkoxy, vi) branched C 3 -C 22 alkoxy; vii) substituted aryl, non-substituted ary, 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 R1 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; R 12 is i) hydrogen, ii) 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; 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 C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit of the formula: (A) v (CH2) and (OCH2CH2) XZ wherein Z is: i) hydrogen, ii) hydroxyl, iii) -CO2H, iv) -SO3-M +, v) -OSO3"M +, vi) C-alkoxy? -C6, vii) substituted aryl, unsubstituted aryl, or mixtures thereof, viii) substituted aryloxy, unsubstituted aryloxy or mixtures thereof, ix) alkyiienamino or mixtures thereof 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, 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 aryloxy, unsubstituted aryloxy, or mixtures thereof; iv) an alkyethyleneoxy 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 cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12, and mixtures of these; Axial units R where each R is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenium. C3-C22 branched alkenyl, or mixtures thereof e) d-C22 alkyl substituted by halogen, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof, f) alkyl of C3-C22 substituted by polyhydroxyl; g) C1-C22 alkoxy; h) branched alkoxy having the formula: Z wherein Z is hydrogen, hydroxyl, C1-C30 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 having the value from 0 to 100, i) substituted aryl, unsubstituted aryl or mixtures thereof, j) substituted alkylenearyl, alkylenearyl not substituted or mixtures thereof: k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof, I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl or mixtures thereof, m) substituted alkylenediaryl and unsubstituted alkylenediaryl, or mixtures thereof; n) thioalkyl C1-C22, branched C3-C22 thioalkyl, or mixtures thereof: o) a carboxylate of the formula O - O- C- R9 where R9 is: i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof ii) CrC22 alkyl substituted with halogen; C3-C22 branched alkyl, C2-C22 alkenylene, branched C3-C22 alkenyl, or mixtures thereof; iii) C3. C22 alkylene substituted by polyhydroxyl, iv) C3-C2 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; 15 xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit with the formula: wherein R10 and R11 are C, C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, > C3-C22 branched alkenyl, or mixtures thereof R12 is i) hydrogen, ii) 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 C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit of the formula: (A) v (CH2) and (OCH2CH2) XZ wherein Z is: i) hydrogen, ii) hydroxyl, ii) -CO2H, v) -SO3-M +, v) -OSO3"M +, vi) alkoxy of Ci-Cß, vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted aryioxy, 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: -OSiR19R20R21, wherein each R19, R20 and R21 is independently i) CrC22 alkyl, branched C3-C22 alkyl, alkenyl C2-C22. C3-C22 branched alkenyl or mixtures thereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof; lii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; V) 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) C-i-Cß alkoxy; g) substituted aryl, unsubstituted aryl, or mixtures thereof; h) substituted aryioxy, unsubstituted aryloxy or mixtures thereof; i) alkyleneamines 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, or mixtures of these. All percentages, ratios and proportions shown in the present invention are given by weight, unless otherwise specified. All temperatures are expressed in degrees Centigrade (° C) unless otherwise specified. All documents cited in this document, are important incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photobleaching compounds and photobleaching compositions. The photobleaching compounds have a maximum wavelength of absorption of Q band of 660 nanometers or greater. The photobleaching and photo-disinfectants of the present invention are phthalocyamines having the formula or naphthalocyanines having the formula: wherein M is a metal or non-photoactive metal, said metal or non-metal chosen from the group consisting of Sn, Ge, Pt, Pd, Pb, P, and mixtures thereof. The phthalocyanine and naphthalocyanine rings consisting of photosensitizers of the present invention, can be substituted with hydrogen or other units described in the thickness of the present document. Surprisingly, the selection of a suitable R1, R2, R3, R4, R5 or R6 substituent is capable of providing the photobleaner or photo-disinfectant with a positive triplet yield of at least 1, preferably at least 10, most preferably at least minus 30, when said portion replaces a hydrogen atom.

In addition, the selection of a suitable portion for a substituent R1, R2, R3, R4, R5 or R6 is also capable of providing a positive change-to-red value of at least 1, preferably a positive change-to-red value of at least 10, most preferably a positive change-to-red value of at least 30, when said portions are replaced by hydrogen. Each unit R1, R2, R3, R4, R5 and R6 is independently: a) hydrogen; b) halogen; c) hydroxyl; d) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof e) C1-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, preferably C1-C4 alkoxy, more preferably methoxy; h) branched alkoxy having the formula: Z or wherein Z is hydrogen, hydroxyl, linear alkyl of C -? - C3o, branched alkyl of C1-C30, alkoxy of d-Cao, -CO2H, -OCH2CO2H, -SO3"M +, -OSO3-M +, -PO32" M , -OPO32"M and 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 and independently having the value of 0 to 6, preferably 0 to 6, each z independently having the value from 0 to 100, preferably from 0 to 10, more preferably from 0 to 3, i) substituted aryl and unsubstituted aryl having the formula: wherein R13 and R14 are independently denatured from the group consisting of hydrogen, d-C6 alkyl, C3-C6 alkenyl, d-Cß alkoxy, C3-C6 branched alkoxy, halogen, -CO2"M +, -SO3" M +, -OSO3"M +, -N (R15) 2 and -N + (R15) 3X ", wherein each R15 is independently hydrogen or alkyl of C? -C4 and mixtures thereof; preferably hydrogen, C1-C6 alkyl, C 2"M +, -S03" M +, -OS03"M + and mixtures thereof, most preferably R 3 or R 14 is hydrogen and the other portion is d-C 6 alkyl, wherein M is a water-soluble cation and X is a water-soluble anion j) substituted alkylenearyl and unsubstituted alkylenearyl having the formula: wherein R 13 and R 14 are as defined above and p is from 1 to about 10 k) substituted aryloxy and unsubstituted aryloxy having essentially the formula: wherein R13 and R14 are as defined above. I) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl units which are defined as portions having the formula: wherein R 3 and R 14 are as defined above and q is from 0 to about 10. m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl having the formula: wherein R13 and R14 are as defined above and w is from about 1 to about 10. n) linear C? -C22 thioalkyl, branched C3-C22 thioalkyl, linear substituted d-C22 thioalkyl, branched C3-C22 thioalkyl substituted and mixtures thereof; o) ester units of the formula -CO2R9 wherein R9 is C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, all of which can be substituted with halogen; C3-C22 polyhydroxy-substituted alkyl, C3-C22 glycol; C1-C22 alkoxy, branched Q3-C22 alkoxy; substituted and unsubstituted aryl, alkylenaryl, aryloxy, oxyalkylenaryl, alkyleneoxyaryl; preferably C1-C22 alkyl > C3-C22 branched alkyl and mixtures thereof; p) alkyleneamino units having the formula: wherein R 10 and R 11 are each a C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 ainnyl, R 12 is hydrogen, C 1 -C 22 alkyl, alkyl Branched C3-C22, C2-C22 alkenyl, branched C3-C22 alkenyl and mixtures thereof, the index v is 0 or 1; X is a water soluble anion, u is from 0 to 22, preferably u is from 3 to about 10. Examples of water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species including chloride, bromide , sulfate, hydrogen sulfate, phosphate and the like; q) an amino unit of the formula: NR17R18 wherein R17 and R18 are each a C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) alkylethylaxy units having the formula: (A) v (CH2) and (OCH2CH2) xZ wherein Z is hydrogen, hydroxyl, -CO2H, -SO3"M +, -OSO3" M +, C6-C6 alkoxy, unsubstituted and substituted aryl, unsubstituted and substituted aryloxy; alkyleneamino as defined hereinabove, or mixtures thereof; the A units comprise nitrogen or oxygen, preferably oxygen; M is a cation soluble in water; v is 0 or 1; x is from 0 to 100, preferably from 0 to 20, most preferably from 0 to 5; and is from 0 to 12, preferably from 1 to 4; however, peroxide-O-O bonds are not contained in the photobleaching compounds of the present invention; s) substituted siloxy and siloxy of the formula -OSiR19R20R21, wherein each R19, R20 and R21 is independently selected from the group consisting of C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, C3 alkenyl -C22 branched or mixtures thereof, substituted or unsubstituted aryl, aryloxy; alkylethylaxy units of the formula: - (A) v - (CH2) and (OCH2CH2)? Z wherein Z is hydrogen, hydroxyl, C 1 -C 30 alkyl, -CO 2 H, -SO 3"M +, -OSO 3" M +, d-C 6 alkoxy; substituted or unsubstituted aryl and aryloxy; alkyleneamino as defined hereinabove and mixtures thereof, preferably hydrogen or d-C6 alkyl, most preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from 0 to about 20, most preferably from 3 to about 10 and (y) is from 0 to 12, preferably from 0 to about 5. The units R1, R2, R3, R4, R5 and R6 are d-C22 alkoxy and halogen, the most preferred R1, R2, R3, R4, R5 and R6 units are C1-C4 alkoxy and halogen. When the unit (Sens.) Is phthalocyanine the most preferred units R1, R2, R3 and R4 are methoxy. When the unit (Sens.) Is naphthalocyanine the units R1, R2, R3, R4, R5 and R6 are chlorine, bromine or iodine.

The compounds useful for the present invention also consist of units R, where R is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl. C3-C22 branched alkenyl, e) halogen-substituted d-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl; f) C3-C22 polyhydroxy-substituted alkyl; g) C1-C22 alkoxy, preferably C1-C4 alkoxy, most preferably methoxy; h) branched alkoxy having the formula: (O)? (CH2) and (OCH2CH2) z Z (0) x (CH2) and (OCH2CH2) z Z wherein Z is hydrogen, hydroxyl, linear alkyl of C? -C30, branched 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 an amount sufficient to satisfy the charge balance, x is 0 or 1, each and independently having the value of 0 to 6, preferably 0 to 6, each z independently having the value from 0 to 100, preferably from 0 to about 10, most preferably from 0 to about 3, i) substituted aryl and unsubstituted aryl having the formula: wherein R13 and R14 are independently selected from the group consisting of hydrogen, d-C6 alkyl, C3-C6 alkenyl, d-Cβ alkoxy, branched C3-C6 alkoxy, halogen, -CO2"M +, -SO3" M +, -OSO3"M +, -N (R15) 2 and -N + (R15) 3X", wherein each R15 is independently hydrogen or C1-C4 alkyl and mixtures thereof; preferably hydrogen, C-Ce alkyl, CO2"M +, -SO3" M +, -OSO3"M + and mixtures thereof, most preferably R13 or R14 is hydrogen and the other portion is C6-alkyl, wherein M is a cation soluble in water and X is a water-soluble anion j) substituted alkylenearyl and unsubstituted alkylenearyl having the formula: wherein R13 and R14 are as defined above and p is from 1 to about . k) substituted aryloxy and unsubstituted aryloxy having the formula: wherein R13 and R14 are as defined above. I) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl units which are defined as portions having the formula: wherein R13 and R14 are as defined above and q is from 0 to about 10. m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl having essentially the formula: wherein R13 and R14 are as defined above and w is from about 1 to about 10. n) linear C1-C22 thioalkyl, branched C3-C22 thioalkyl, linear substituted C1-C22 thioalkyl, substituted branched C3-C22 thioaicyl substituted and mixtures thereof; o) carboxylate units of the formula O - O- C- R9 wherein R9 is d-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, all of which may be substituted with halogen; C3-C22 polyhydroxy-substituted alkyl, C3-C22 glycol; C1-C22 alkoxy, branched C3-C22 alkoxy; substituted and unsubstituted aryio, alkylenearyl, aryloxy, oxyalkylenearyl, alkyleneoxyaryl; preferably C 1 -C 22 alkyl, branched C 3 -C 22 alkyl and mixtures thereof; p) alkyleneamino units having the formula: wherein R10 and R1 are each a C? -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, branched C3-C22 alkenyl and mixtures thereof, the index v is 0 or 1; A is -O-of -NH; X is a water soluble anion, u is from 0 to 22, preferably u is from 3 to about 10, in case v is 1, then u would be greater than or equal to 1. Examples of water soluble anions include species organic such as fumarate, tartrate, oxalate and the like, inorganic species including chloride, bromide, sulfate, hydrogen sulfate, phosphate and the like; q) an amino unit of the formula: NR17R18 wherein R17 and R18 are each a C-1-C22 alkyl. C3-C22 branched alkyl, C2-C22 alkenyl > C3-C22 branched alkenyl or mixtures thereof; r) alkylethylaxy units having the formula: (A) v (CH2) and (OCH2CH2) x Z wherein Z is hydrogen, hydroxyl, -CO2H, -SO3"M +, -OSO3" M +, d-C6 alkoxy, unsubstituted and substituted aryl, unsubstituted and substituted aryloxy; alkyleneamino as defined hereinabove, or mixtures thereof; the A units comprise nitrogen or oxygen, preferably oxygen; M is a cation soluble in water; v is 0 or 1; x is from 0 to 100, preferably from 0 to 20, most preferably from 0 to 5; and is from 0 to 12, preferably from 1 to 4; however, peroxide-O-O bonds are not contained in the photobleaching compounds of the present invention; s) substituted siloxy and siloxy of the formula -OSiR19R20R21, wherein each R19, R20 and R21 is independently selected from the group consisting of C? -C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, C3-C22 branched or mixtures thereof, aryl and substituted or unsubstituted aryloxy; alkylethylaxy units of the formula: (A) v (CH2) and (OCH2CH2) x Z wherein Z is hydrogen, hydroxyl, d-C3o alkyl, -CO2H, -SO3"M +, -OSO3" M +, d-C6 alkoxy; substituted or unsubstituted aryl and aryloxy; alkyleneamino as defined hereinabove and mixtures thereof, preferably hydrogen or d-C6 alkyl, most preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from 0 to about 20, most preferably from 3 to about 10 and (y) is from 0 to 12, preferably from 0 to about 5. In accordance with the present invention, preferred axial R units they comprise portions that have the formula: wherein Y is a linker portion selected from the group consisting of O, CR25R26, OsR25R26, OsnR 5R26 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 C1-C30 alkyl, branched C3-C30 alkyl, linear C2-C30 alkenylene, branched C3-C30 alkenyl, C6-C2 aryl, C7-C2 arylalkyl, C7-C20 alkylaryl and mixtures of the same; b) an alkylethyleneoxy unit of the formula: - (R23) and (OR22) xOZ wherein Z is selected from the group consisting of hydrogen, d-C2o alkyl > branched C3-C20 alkyl, linear C2-C20 alkenyl, branched C3-C2o alkenyl, C6-C2o aryl, C7-C30 arylalkyl, C6-C2 alkylaryl and mixtures thereof; R22 is selected from the group consisting of linear C1-C4 alkylene, branched C3-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, C3-C3 arylalkylene, C7-C30 alkylarylene and mixtures thereof; x is from 1 to 100; and is O 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 alkenylene of C3-C3o branched, arylene of Ce-Cie and mixtures thereof; W is selected from the group consisting of -CO2"M +, -S03" M +, -OSO3"M +; PO 2" M +, -OPO3"M +, -N + (R27) 3X"; wherein R 27 is independently hydrogen, d-C 6 alkyl, - (CH 2) n OH, - (CH 2 CH 2 O) n H and mixtures thereof; where n is from 1 to 4; M is a cation soluble in water of sufficient charge for provide electronic neutrality and X is a water soluble anion as defined hereinbefore. 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 alkyl, branched C3-C2o alkyl, alkenyl of linear C2-C2o, alkenyl of C3-C20 branched, C6-C10 aryl, C -C20 arylalkyl, C7-C2 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, Ce-Cile arylene and mixtures thereof; x is from 1 to 50; and is 0 6 1. The most preferred axial R units comprise and equal to 0, Z is hydrogen, C1-C20 alkyl, branched C3-C20 alkyl, Ce-C20 aryl and mixtures thereof, most preferably Z is hydrogen or linear C6-C2o alkyl, branched C10-C20 alkyl; R22 is linear C1-C4 alkylene or branched C3-C4 alkylene. R units which are also preferred have the formula: Y i -Qj wherein 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: _R2 __W wherein R24 is selected from the group consisting of linear C2-C20 alkylene, branched C3-C20 alkylene, linear C2-C20 alkenylene, branched C3-C20 alkenylene, C6-? arylene, and mixtures thereof; W is selected from the group consisting of -CO2"M +, -SO3" M +, -OSO3"M +, PO32" M +, -OPO3"M +, -N + (R27) 3X"; wherein R27 is independently hydrogen, C ^ -CQ alkyl, - (CH2) nOH, - (CH2CH2?) nH and mixtures thereof; where n is from 1 to 4; M is a water-soluble cation of sufficient charge to provide electronic neutrality and X is a water-soluble anion as defined hereinabove. A preferred hydrophilic R has the index i equal to 1; R24 is a linear C3-C22 alkylene, branched C3-C2o alkylene; W is -C? 2_M +, -SO3"M +, -OSO3" M +; M is a cation soluble in water of sufficient charge to provide electronic neutrality. Examples of Y units suitable for use in R units have the formula: they have the formula - O - K1, - Sn - K1, - OSn - K1 where i is equal to 1 and j equals 1. Other examples have the formula? l? l - Si- K2 - OSi- K2 ¿3 'í (3 where i is equal to 1 and j equals 3. The above examples also apply to units Y when used with ionic portions Q. When the compounds of the present invention have one or more substituent units R1, R2, R3 and R4 present, as in the case of phthalocyanine, or units R1, R2, R3, R4, R5 and R6 as in the case of naphthalocyanines, the exact orientation of the substituents may not be exactly known. However, for the purposes of the compounds of the present invention, there are certain equivalencies of substitution. For example, the two units of the following formula which contain the same substitution R1 are equivalent for the purposes of the present invention and the selection of any structure on the other will not affect the desired properties of the molecule described in this document. In addition, the compounds containing the substitution represented by the following formulas which contain the same substitutions of unit R1 and R2, are also equivalent for the purposes of the present invention and the selection of any of the structures on the other will not affect the desired properties of the molecules described herein. However, the above examples are only representative of the total number of examples of equivalent structure that will be recognized by those skilled in the art. The compounds useful for the present invention having one or more units R1, R2, R3 and R4, substituted, as in the case of phthalocyanine, or units R1, R2, R3, R4, R5 and R6, as in the case of naphthalocyanines, which they have their substitutions oriented in a way described by the following formula they are not equivalent for the purposes of the present invention and each would constitute separate compounds without taking into account the fact that the units R1 and R2 are equivalent. The above examples do not exhaust the number of possible non-equivalent structures using any combination of units R1, R2, R3, R4, R5 and R6 recognized by those skilled in the art. The axially R units that can be used are directly connected to the central tin, germanium, platinum or palladium atom. Each R unit can be chosen independently of the other. The selection of a unit R is done, for example, to provide solubility, not solubility, "substantivity", "no substantivity" to the compound. These are some examples of the usefulness of the axial group and those skilled in the art will recognize that other properties of the photobleaching agents can be controlled by axial substitution. The R units are nonionic, cationic, or anionic. The following is an example of a preferred "substantive" modality (it has an affinity for the surfaces, for example fabrics) of the present invention consisting of a phthalocyanine ring system wherein at least one of the units R1, R2, R3 and R4 of each aromatic portion is methoxy, each R group consists of an ethyleneoxy unit of the formula where for each unit R Z is methoxy and X is 7.2 thus providing the portion with an average ethoxylation value of 7.2.

Below is an example of a "substantive" modality (has an affinity for the surfaces, for example fabric) of the present invention which consists of a phthalocyanine ring system wherein at least two of the units R1, R2, R3 and R4 of each aromatic portion is methoxy, each group R it consists of an ethyleneoxy unit of the formula - (OCH2CH2) xZ where for each unit RZ is methoxy and X is 7.2 thus providing the portion with an average ethoxylation value of 7.2.

An example of a "non-substantive" mode is given below (the charged R units reduce the affinity for the surfaces, for example fabric) of the present invention consisting of a naphthalocyanine ring system where at least 2 of the units R1, R2, R3, R4, R5 and R6 of each aromatic portion are chloro, a group R consists of a siloxy unit of the formula -OsiR7R8R9 where the units R7 and R8 are methyl and R9 is of the formula: - (CH2) yZ where Z is -SO3-M +, M is sodium and y is equal to 6; the second axial unit R is methoxy.

An example of a "non-substantive" mode is given below (the charged R units reduce affinity for surfaces, eg, fabrics) of the present invention consisting of a naphthalocyanine ring system where at least one of the units R1, R2, R3, R4, R5 and R6 of each aromatic portion is bromide, and the R groups consist of a siloxy unit of the formula -OSiR7R8R9 where the units R7 and R8 are methyl and R9 is of the formula - (CH2) and Z. where Z is -SO3-M +, M is sodium and y is equal to six.

The compounds of the present invention can be modified to have a wide range of surface affinities, the molecules can be made "substantive" or "non-substantive" by the choice of axial R units. The term "substantivity" as defined herein, is the property that allows the photobleaching agent to deposit satisfactorily on a target surface. For example, the axial R groups, defined below in the specification, may be chosen to provide compatibility of the photobleaching compound with a synthetic fabric, a hard surface such as a ceramic mosaic or in general any fabric, article of manufacture or site that is objective of photobleaching. The present invention also relates to detergent compositions for laundry or hard surface cleaning consisting of: A) At least about 0.1%, preferably close to 0. 1% to about 30%, most preferably from about 1% to about 30%, very much preferably from about 5% to about 20% by weight, of a detersive surfactant, said detersive surfactant is selected from group consisting of anionic, cationic, zwitterionic nonionic, ampholytic surfactants and mixtures thereof; B) At least about 0.001 ppm, preferably about 0.01 about 10000 ppm, most preferably about 0.01 about 5000 ppm, very much preferably about 10 about 1000 ppm, of a photosensitizing compound having a maximum wavelength of Q band absorption of 660 nanometers or greater in accordance with the present invention; and C) The rest of the vehicle and auxiliary materials. The present invention also relates to detergent compositions for laundry or hard surface cleaning consisting of: A) At least about 0.1%, preferably from 0.1% to about 30%, most preferably about 1% about of 30%, most preferably about 5% about 20% by weight of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants and mixtures of these. B) At least about 0.001 ppm, preferably about 0.01 about 10000 ppm, most preferably about 0.1 about 5000 ppm, very much preferably from about 10 to about 1000 ppm, of a photosensitizing compound having a maximum wavelength of Q band absorption of 660 nanometers or greater in accordance with the present invention; wherein the choice of a suitable portion for the substituent R1, R2, R3, R4, R5 or R6 is capable of providing the photobleaner or photo-disinfectant with a positive field Amp of at least 1, preferably at least 10, most preferably at least minus 30, when said portion replaces a hydrogen atom; and C) The rest of the vehicle and auxiliary materials. The present invention also relates to laundry detergent and hard surface cleaning compositions consisting of: A) At least about 0.1%, preferably about 0.1% about 30%, most preferably about 1% about 30%, very much preferably 5% about 20% by weight, of a detersive surfactant, said detersive surfactant is selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic, and mixed surfactants of these; B) At least about 0.001 ppm, preferably about 0.01 about 10000 ppm, most preferably about 0.1 about 5000 ppm, most preferably about 10 about 1000 ppm, of a photosensitizing compound having a length wavelength of maximum band Q absorption of 660 nanometers or greater in accordance with the present invention; where the selection of an adequate portion of a substituent R1, R2, R3, R4, R5 or R6 is capable of providing a positive change-to-red value of at least 1, preferably a positive change-to-red value of at least 10, most preferably a positive value of change to red of at least 30, when said portions are replaced by hydrogen; C) The rest of the vehicle and auxiliary materials. The selection of a specific R-portion is generally done to adjust the solubility or substantivity of the molecule. For example, the unit R is compared to the structural properties of the target material (i.e. fabric) or the target substrate (i.e., spots). The option to design the properties of the R unit for the material is due to the ability to choose R units independently of affecting the phthalocyanine or naphthalocyanine ring. An additional benefit of the photobleaching system of the present invention is that they generally take better care of fabrics and color than conventional bleach (i.e., hypochlorite). The "non-substantive" molecules are desirably for applications where the photosensitizing compound should remain in the laundry water instead of being attracted to a particular surface, ie water sterilization. The term "low tint" as used herein, and throughout the specification refers to photobleaners having a? Ma? Of their upper Q band about 700 nm and therefore are slightly perceptible to the human eye. These additional materials of the present invention that have maximum wavelengths of Q band on the scale "visible", (ie 660-700 nanometers) are materials that are more suitable when the perception of a material with color is not important in terms of deterioration. Effective photobleaching is predicted in the production of a singlet oxygen molecule, a theory that has been extensively studied and understood by those skilled in the photobleaching technique. Because the singlet oxygen species are short lived, it is very important that the photosensitizing molecule is close to the spot or the microbe that will be "attacked". The molecules of the present invention, due to the ability of the formulator to control "the substantivity", can be directed to any desired surface. The additional ability to prevent layering and stacking of photosensitizing molecules due to the axial nature of the R units, provides an efficient monolayer. For example, one embodiment of the present invention for removing stains from a fabric will have the requirements that the photosensitizing organotin, organogermanium, organoplatinum, organopalladium, organoplomo, or organophosphorus compound have an affinity for the surface of the fabric, and that the Photobleaching compound is close to the desired site of action. These requirements are achieved by manipulating one or more R units.

The present invention also relates to a process for developing a photosensitized reaction or a catalyzed singlet oxygen reaction, wherein one or more phthalocyanine compounds, or naphthalocyanine in the presence of oxygen, come into contact with the medium in which the said reaction will be carried out, or incorporated in this medium, or irradiated with light. It has long been known that phthalocyanine and naphthalocyanine rings can absorb quanta of light and form electronically excited species (in singlet and triplet) and that these species can be extinguished by oxygen to produce "excited oxygen species". A particularly preferred "excited oxygen species" is singlet oxygen which is the most reliable formed by the quenching of the triplet state of a photosensitizer, such as a phthalocyanine by molecular oxygen. Therefore it is an objective of the formulator of the photobleach to produce compounds that favor the formation of the triplet state. When a photosensitizer is irradiated with light, the state of the resulting singlet energy goes through a variety of processes, ie a re-emission of light (fluorescence). The most important process with respect to photobleaching via oxygen in singlet is the intersystem crossing (ISC). That mechanism by which the singlet status is converted to the triplet state. In general, the efficiency of this process is analyzed in terms of quantum performance, that is, the number of photons that are absorbed that lead to the desired triplet excited state. The present invention provides enhanced photobleaching by modifying the efficiency of the intersystem crossing from the singlet state to the triplet state.

The formulator can modify the molecules of the present invention to increase the quantum efficiency of triplet formation via "heavy atom effect". The selection of a portion for its "heavy atom effect" can be done independently for other factors, for example, without taking into account the solubility factors. This is because the choice of axial R groups for solubility will not be accommodated in the changes made to the phthalocyanine or naphthalocyanine system. The determination of the wavelength value of the Q band and if a change in this wavelength occurs when a particular portion (unit R1, R2, R3, R4, R5 or R6) replaces a hydrogen atom in the ring Phthalocyanine or naphthalocyanine directly. Typically, a solution having a concentration of about 1x10-6 M of phthalocyanine or naphthalocyanine to be measured is prepared using a suitable solvent (for example dimethylformamide) containing 1% by weight of triton X-100. A UV / visible spectrum is obtained and the Q band max is recorded. This value is the "? S-ma? Substrate". A spectrum for the material is obtained in the same way before the introduction of the substituent group. This value is the "? R-max reference". The two spectra are compared and the resulting measured values are placed in the following equation wavelength of change to red = ?? max =? S-max-? R-max where if the obtained number is greater than or equal to 1, then the substituent group has produced a positive change to red of at least one nanometer and the substituent is a preferred embodiment of the present invention. If the material of interest is not soluble in dimethylformamide another suitable solvent may be used. The quantum yield energies and the excited state are well known to those skilled in the art and methods for determining the yield of triplet quants and similar photophysical parameters are described in depth in the following Bonnet references. R .; McGarvey, D.J .: Harriman. TO.; Land, E: J :; Truscott, T.B .; Winfield, U-J. Photochem. Photobiol. 1988, 48 (3), pg. 271-6; Davila. J., Harriman, A., Gulliya, K.S., Photochem. Photobiol., 1991, 53 (1), pg. 1-11; Davila, J., Harriman, A., Photochem. Photobiol., 1989, 50 (1), pg. 29-35; Charlesworth. P., Truscottt, T.G., Brooks, R.C., Wilson, B.C., J. Photochem. Photobiol., Part B 994, 26 (3), PG. 277-82; Zhang, X., Xu., H., J.Chem. Soc, Faraday Trans., 1993, 89 (18), pg. 3347-51; Simpson, M.S.C., Beeby, A., Bishop, S.M., MacRobert, A.J., Parker, A.W., Phillips, D., Proc. SPIE - //? F. Soc. Opt. Eng., 1992, 1640, pg. 520-9; Phillips, D., Puré Appl. Chem. 1995, 67 (1), pg. 117-26; Wilkinson, F., Helman, W.P., Ross, A.B., J.Phys. Chem. Ref. Data, 1993, 22 (1), pg. 113-262; Lever, A.P.B., Licoccia, S., Magnell, k., Minor, P.C., Ramaswamy, B.S., Adv. Chem. Ser., 1982, 201, pg. 237-52; West, M.A., Creat. Detect. Excited State, 1976, 4, pg. 217-307; Ford, W.E., Rihter, B.D., Kenney, M.E., Rodgers, M.A. J., Photochem. Photobiol., 1989, 50 (3), pg. 277- 282; Firey, P.A., Ford, W.E., Sounik, J.R., Kenney, M.E., Rodgers, A.J.R., J.Am. Chem. Soc, 1988, 110, pg. 7626-7630; Firey, P.A., Rodgers, M.A.J., Photochem. Photobiol., 1987, 45 (4), pg. 535-8; all these are incorporated by reference in their entirety. For the purposes of the present invention, delta triplet yield is determined by determining the yield percentage of triplet quants for phthalocyanine or naphthalocyanine of interest and this is the term ftpp-substrate- The percent yield of triplet quanta for phthalocyanine or naphthalocyanine before the introduction of the substituent is determined. This value is ftrip-reference. The value is placed in the following equation performance increase of quanta in state of Ftrip-substrate-Ftpp-reference When the value for? Ftr¡p a number greater than or equal to 1, the substitution made for a hydrogen atom in the unit (Sens.) Of the photosensitizer is a preferred embodiment of the present invention. . In particular, the present invention relates to a process for bleaching or removing stains for textiles, organic or inorganic substrates. Another object of the present invention is to protect the latter against the attack of microorganisms, where the substrates are treated with phthalocyanines or naphthalocyanines of the present invention, in the presence of water and while irradiating light.

Another advantage of the present invention is the fact that each unit R can be directed towards a separate desired property and the molecules of the present invention can therefore be thought of as "prosecuted." For example, one axial R unit may be directed toward increased solubility while another axial R group may be chosen for the ability to provide increased substantivity. The present invention also relates to a process for developing a photosensitized reaction or an oxygen catalyzed singlet reaction, wherein one or more compounds of phthalocyanine or naphthalocyanine in the presence of oxygen are brought into contact with the medium in which or on the that said reactions will be carried out, or incorporated in this medium are irradiated with light. If the method is developed in an aqueous medium (for example textile sterilization), irradiation with light can be developed directly in the treatment medium by an artificial source of light mounted inside or outside the medium or in the substrates, in a state wet, it can subsequently be irradiated, again by an artificial source of light, or it can be exposed to sunlight. Good antimicrobial effects of the compounds present even at very low concentrations of active substance, for example at 0.001 ppm, can be achieved. Depending on the field of use and the phthalocyanine or naphthalocyanine derivatives used, a concentration between 0.005 and 100, preferably 0.01 and 50 ppm. The irradiation can be carried out by means of an artificial source of light or by means of sunlight. The intensity of illumination can vary within wide limits, and depends both on the concentration of the active as well as the nature of the light source as well as the photobleaching efficiency of any particular compound of the present invention. Another parameter that can vary is the exposure time, that is, to obtain the same effect, exposure must be longer at a lower intensity of light than at a higher intensity. In general, depending on the field of use, the exposure time ranges from a few minutes to a few hours. If the process takes place in an aqueous medium (for example the sterilization of textiles), irradiation with light can be developed directly in the treatment medium, by means of an artificial source of light mounted inside or outside the medium, or the articles, in a wet state, they can subsequently be irradiated, again by means of an artificial source of light, or they can be exposed to sunlight. Good antimicrobial effects can be achieved even with low concentrations of the active substance, for example at 0.001 ppm. Depending on the field of use and on the phthalocyanine or naphthalocyanine derivative used. A concentration between 0.05 and 2000, preferably 0.01 and 1000 ppm is preferable. The methods of the present invention can also be achieved in carriers based on solvents or in low aqueous solutions. For the purpose of the present invention the term "low aqueous" means that water is added to a carrier system to modify the properties of the carrier and not solely for the purpose of solubilizing the substrate. For example, solvents that are capable of maintaining solubilized oxygen as well as forming a water-miscible system are preferred. Some non-limiting examples of these solvents are butoxypropoxypropanol (BPP), methoxypropoxypropanol (MPP), ethoxyproxypropanol (EPP), and propoxypropoxypropanol (PPP). The embodiments of the present invention consisting of these non-classical aqueous compositions are most useful when the photobleach is to be applied to fabrics or woven surfaces containing agents that repel water and moisture. The sterilization of textiles of synthetic or natural origin can be mentioned as an important application. Thus, the material to be washed at home or in the industry can be disinfected by the methods of the present invention. The material to be washed can be treated for this purpose in the manner mentioned above with aqueous solutions of phthalocyanines or naphthalocyanines of the present invention while irradiating with light. It is of great benefit that phthalocyanine and naphthalocyanines are present in the treatment medium at a concentration of 0.01 to about 2000 mg per liter, preferably from 0.1 to 1000, most preferably from 1 to 500. Sterilization can be profitably developed together with the washing process. For this purpose, the material to be washed is treated with a washing medium containing custom detergent substances, one or more phthalocyanines or naphthalocyanines according to the present invention, and if desired, inorganic salts and / or other auxiliary materials having antimicrobial properties. The washing process can be carried out manually, for example in a tub, or it can be developed in a washing machine. The necessary exposure to light can be carried out during the washing process by suitable light sources, or the wet material that is being washed also, can subsequently, for example during drying, either be exposed to a suitable artificial source of light or simply exposed to sunlight, for example during drying. Surface bleaching can be achieved, for example by applying to the appropriate surface, an aqueous solution of a phthalocyanine or naphthalocyanine compound according to the present invention, this solution preferably consisting of about 0.001 to about 10% by weight of an active substance. The solution can also contain, in addition, other customary additives, for example wetting agents, dispersing or emulsifying agents, detergent substances and, if desired, inorganic salts. After applying this solution, the surface is simply exposed to sunlight, or, if required, it can also be irradiated by an artificial source of light. It is advisable to maintain surface moisture during exposure to light. The laundry compositions of the present invention optionally consist of detersive surfactants, examples of which are anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, however, the formulator is not limited by these examples or combinations thereof. The surfactants are present from about 0% to about 95%, preferably from about 5% to about 30% by weight of the composition. The cleaning compositions of the present invention optionally consist of detersive surfactants, examples of which are anionic, cationic nonionic, amphoteric and zwitterionic surfactants, however, the formulator is not limited to these examples or combinations of these. Surfactants are present from about 0% to about 50%, preferably from about 5% to about 30% by weight of the composition. The laundry compositions of the present invention optionally contain detergency builders, examples of these are silicates, carbonates, and zeolites, however the user is not limited to these examples or combinations of these. Builders are present from about 0% to about 95%, preferably from about 5% to about 30% by weight of the composition. The cleaning compositions of the present invention optionally contain detergency builders, examples of these are silicates, carbonates, and zeolites, however the user is not limited to these examples or combinations of these. Builder agents are present from about 0% to about 50%, preferably from about 5% to about 30% by weight of the composition. The hard surface cleaner of the present invention optionally contains builders, examples of these are silicates, carbonates, and zeolites, however, the user is not limited to these examples or combinations thereof. The detergency builders are present from about 0% to about 50%, preferably from about % to about 30% by weight of the composition. The hard surface cleaner of the present invention optionally contains abrasives of about 0.5% about 85%, preferably from about 10% to about 85% by weight of the composition.

Suitable abrasives are silicates, carbonates, perlite, clay and pulverized ceramic clay, however, the user is not restricted to these examples or combinations of these. Substances that increase the action can also be added in the process according to the invention, among them electrolytes, for example organic salts, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate., sodium acetate, ammonium acetate, alkali metal phosphates and alkali metal tripolyphosphates, especially sodium chloride and sodium sulfate. These salts can be added to the agents according to their invention or they can be added directly to the application method, so they are present in the application solution in a concentration of, preferably 0.1 to 10%, by weight. What is meant by the term aqueous solution is a solution that is essentially water, however, the formulator may include auxiliary materials as well as a surfactant to aid in the removal of "treated" microorganisms during rinsing or cleaning Subsequent The presence of an aqueous solution facilitates the production of a singlet oxygen due to the higher concentration of oxygen in water than in air.

Surfactant The instant cleaning compositions contain from about 0.1% to about 60% by weight of a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface active agents. For liquid systems, the surfactant is preferably present in an amount of about 0.1% to 20% by weight of the composition. For solid (ie granular) and viscous semi-solid (i.e., gels, pastes, etc.) systems, the surfactant is preferably present in an amount of about 1.5% to 30% by weight of the composition. Some non-limiting examples of surfactants useful in this invention typically at levels of about 1% to about 55% by weight, include the conventional Cn-Cis alkylbenzene sulphonates ("LAS") and primarily, C10-C20 alkyl sulphates ( "AS") of branched and random chain, the secondary alkyl sulfates (2,3) of C10-C18 of the formula CH3 (CH2) x (CHOS? 3"M +) CH3 and CH3 (CH2) and (CHOS? 3" M + ) CH2CH3 where xy (y + 1) are integers of at least about 7, preferably at least about 9, and M is a cation soluble in water, especially sodium, unsaturated sulfates such as oleyl sulfate, C10-C18 alkylalkoxy sulfates ("AEXS", especially ethoxysulfates of 1-7 EO), alkylalkoxycarboxylates C10-C18 (especially the ethoxycarboxylates 1-5 EO), the glycerol ethers of C10-C18 the C10-C18 alkyipoliglucosides and their corresponding sulphated polyglucosides, and the alpha sulfonated fatty acid esters of C? 0-C? 8. If desired, conventional non-ionic and amphoteric surface-active agents such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow-alkylethoxylates and the C6-C12 alkylphenolalkoxylates. (especially ethoxylates and ethoxy / propoximyxtes), betaines and sulfobetaines of Ci2-C? 8 ("sultaines"), C10-C18 amino oxides and the like can also be included in the compositions in general. C10-C18 polyhydroxy fatty acid N-alkyl alamides can also be used. Typical examples include the N-methylglucamides of C12-C 8. See WO 9,206,154. Other surfactants derived from sugar include polyhydroxy fatty acid N-alkoxyamides, such as C10-C18 N- (3-methoxypropyl) glucamide. The glucocides of C12-C 8 N-propyl to N-hexyl can be used for low foaming. Conventional C10-C20 soaps can also be used. If high foaming is desired, branched-chain C10-C16 soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are those described later in this docu and are listed in standard texts.

The anionic surfactants can be broadly described as 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 one radical chosen from the group consisting of radicals of suifonic acid and sulfuric acid ester. (The alkyl portion of high acyl radicals is included in the term alkyl). Important examples of anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are sodium or potassium alkyl sulfates, especially those obtained by sulfatar high alcohols (C8-C18 carbon atoms) produced by reducing the glycerides of bait or coconut oil; sodium or potassium alkylbenzene sulphonates, 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); Sodium alkyl glyceryl ether sulfates, especially those ethers of high alcohols derived from bait and coconut oil, monoglyceride sulfates of coconut oil fatty acids and sulfonates; Sodium or potassium salts of sulfuric acid ester of the reaction product of a mole of a high fatty alcohol (for example bait or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of ethylene oxide-alkylphenol ether sulfates with from about one to about ten ethylene oxide units per molecule and wherein the alkyl radicals contain from 8 to 12 carbon atoms. carbon; The products of the reaction of fatty acids are derived from sodium or potassium salts of coconut oil of fatty acid amides of a methyl tauride in which fatty acids, for example, are derived from coconut oil and beta-acetoxy of sodium or potassium or beta-acetamido-alkanesulphonates where the alkane has from 8 to 22 carbon atoms. Additionally, the secondary alkyl sulphates can be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between the sulfated surfactants and the conventional alkyl sulfate surfactants. The following are non-limiting examples of such ingredients. Conventional primary alkyl sulfates (LAS), as illustrated above, have the general formula ROSO3-M + where R is typically a linear C8-22 hydrocarbyl group and M is a cation soluble in water, for example sodium LAS. Branched chain primary alkyl sulfate surfactants (ie, branched chain "PAS") having 8 to 20 carbon atoms are also known, see, for example, Eur. Pat. Sun. 439,316, Smith, et al., Issued January 21, 1991. Conventional secondary alkyl sulfate surfactants are those materials having the sulfate portion distributed randomly along the hydrocarbyl "base structure" of the molecule. Such materials can be described by the structure CH3 (CH2) n (CHOS? 3-M +) (CH2) mCH3 where m and n are integers of two or more and the sum of m + n is typically about 9 to 17, and M is a cation soluble in water. The secondary alkyl sulfates mentioned above are those that are prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is described in the patent of E.U.A. No. 3,234,258, Morris, issued February 8, 1996 or in the patent of E.U.A. No. 5,075,041, by Lutz, issued on December 24, 1991. The synthesis conducted in solvents exhibited by secondary alkyl sulphates (2, 3) upon cooling, results in products in which by purifying them to remove unreacted materials, randomly sulfated materials, non-sulfated byproducts such as C10 alcohols and higher, secondary olefin sulfonates, and the like, typically are 90 +% pure mixtures of sulfated materials 2- and 3- (some sodium sulfates may be present) and are white, non-tacky, apparently crystalline, solid. Some 2,3-disulfates may also be present, but generally consist of no more than 5% of the mixture of secondary (2,3) alkyl mono-sulfates. Such materials are available under the name "DAN", for example, "DAN 200" from Shell Oil Company.

Bleaching agents and bleach activators The detergent compositions described herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of about 1% to about 30%, very typically from about 5% to about 20%, of the detergent compositions, especially for fabric laundry. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of bleaching compositions that consist of bleaching agent plus bleach activator. . The bleaching agents used in this invention can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning or other cleaning purposes that are known or will be known. These include oxygen bleaches other than hypohalite bleach (e.g. hypochlorite). Perborate whiteners (e.g. mono- or tetrahydrate sodium salts) and percarbonate bleach can also be used in the invention. Another category of bleaching agent that can be used without restriction includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include monoperoxyphthalate magnesium hexahydrate, the magnesium salt of the acid metabenzene perbenzoic, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching agents are described in the U.S.A. No. 4,483,781, Hartman, issued November 20, 1984, patent application of E.U.A. 740,446, Burns et al., Filed June 3, 1985, European patent application no. 0,133,354, Banks and others, published February 20, 1985, and the patent of E.U.A. do not. 4,412,934 to Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. do not. 4,634,551, issued June 6, 1987 to Burns et al. Peroxygen bleaching agents can also be used. Peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (for example OXONE, commercially manufactured by DuPont) can also be used. A preferred percarbonate bleach consists of dry particles having an average particle size in the range of about 500 micrometers to about 1000 micrometers, no more than about 10% by weight of said particles being smaller than about 200 micrometers and no more than about 10% by weight of said particles being larger than about 1250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants.

Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, perborates, percarbonates, etc. they are preferably combined with bleach activators, leading to on-site production in an aqueous solution (ie, during the washing process) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are described in the patent E.U.A. do not. 4,915,854, issued April 10, 1990 by Mao et al., And in the U.S. patent. do not. 4,412,934. Activators of nonanoyloxybenzene sulphonate (NOBS) and tetraacetylene ethylene diamine (TAED) are typical, and mixtures of these can also be used. See also document E.U.A. do not. 4,634,551 to obtain other bleaches and activators useful in this invention. Preferred bleach activators derived from preferred amides are those containing the formulas: R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L where R1 is an alkyl group containing about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryio or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable residual group. A residual group is any group that moves from the bleach activator as a result of a nucleophilic attack on the activator of bleaching by the perhydrolysis anion. A preferred residual group is phenyl sulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in the US Pat.

E.U.A. do not. 4,634,551, incorporated herein by reference. Another class of bleach activators consists of benzoxazine type activators described in the U.S. patent. do not. 4,966,723 to Hodge et al., Issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazine type is: Another class of preferred bleach activators includes acylactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: where R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 2,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undeenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam and mixtures thereof. See also patent E.U.A. number 4,545,784 issued to Sanderson on October 8, 1985, incorporated herein by reference, which describes acylcaprolactams, including benzoylaprolactam, is absorbed in sodium perborate. As a practical matter, and in no way limiting, the compositions and methods included in this document can be adjusted to provide in the order of at least one part per ten million species of active bleach catalyst in an aqueous wash solution, and preferably it will provide about 0.1 ppm to about 700 ppm, most preferably from about 1 ppm to about 500 ppm, of the catalyst species in the wash solution. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in this invention. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulphonated phthalocyanines of zinc and / or aluminum. See the patent of E.U.A.

No. 4,033,718, issued July 5, 1977 to Holcombe et al. In case of using them, detergent compositions will typically contain close to 0. 025% to about 1.25% by weight of such bleaches, especially phthalocyanine sodium sulfonate PH Regulators The pH regulators can be included in the formulations of this invention for a variety of purposes. One such purpose is to adjust the cleaning surface pH to optimize the effectiveness of the hard surface cleaning composition relative to a particular type of stain. The pH regulators can be included to stabilize the auxiliary ingredients with respect to life is so widespread or for the purposes of maintaining compatibility between various aesthetic ingredients. The hard surface cleaner of the present invention optionally contains pH adjusters to adjust the pH in a range of about 7 to 13 wax, preferably about 8 to 13 wax, most preferably from about 10 to about 11. Some non-limiting examples of such suitable pH regulators are sodium carbonate, sodium carbonate and sodium bicarbonate, however, the regulator is not restricted to these examples or combinations of these.

AUXILIARY MATERIALS The compositions described herein may optionally include one or more auxiliary detergent materials or other materials to assist or improve the cleaning performance, treatment of the surface to be cleaned, or modify the aesthetics of the composition (for example perfumes, dyes, inks, etc). Illustrative examples of such auxiliary materials are shown below but are not intended to be exclusive or to limit scope.

Chelating Agents The detergent 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 claiming to be limited by theory, it is thought that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions by forming soluble chelators. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylene tetraaminohexaacetates, diethylenetriaminepentaacetates and ethanol diglycins, the alkali metal, ammonium and substituted ammonium salts described herein, and mixtures thereof. Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferred are those amino phosphonates which do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See Patent of E.U. 3,812,044, of May 21, 1974, to Connor and others. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. 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 they are used, 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%.

Abrasives An essential component for many solid or semi-solid viscous hard surface cleaning compositions is the abrasive material that is added to facilitate the polishing action. Abrasive polishing cleaners provide convenient and useful means to develop the sanitization of porcelain and tile surfaces, especially bathtubs, showers and toilets. The particle of abrasive material within such compositions serves to abrade and release stains adhering to hard surfaces and further serves to create a closer contact between hard surface stains and the surfactant and / or bleaching agents also present in the compositions of cleaning. The abrasive cleaners traditionally contain mineral material of water-insoluble particles, relatively hard as an abrasive agent. The most common of such abrasive agents is finely divided silica sand having a particle size ranging from about 1 to 300 mirrors and a specific gravity of about 2.1 or higher. While such material is generally very effective in polishing spots on the treated surfaces, abrasive material of this type tends to be difficult to rinse from the toilet, shower or surface of the tub. In this case where moderate or highly water soluble abrasive material (sodium carbonate) is required, imidod sulfate can be used as the sole abrasive or it can be added in parts.

It has also been discovered that abrasive compositions of this desired type can be made using a particular type of expanded perlite abrasive in combination with the surfactants, fillers and other optional polishing material ingredients listed herein. The abrasive materials suitable in the present invention are those which are contained in the patent of E.U.A. number 4,051, 056, Hartman, issued September 27, 1977 and included in this document by reference.

Perfume Perfumes are an important ingredient especially for the liquid composition modality. The perfume is usually used at levels of 0% to 5%. In the patent of E.U.A. No. 4,246,129, Kacher, issued January 20, 1981 (incorporated herein by reference), describes certain perfume materials that perform the added function of reducing the solubility of the anionic sulfonate and sulfate surfactants.

Dyes Dyes may be included in levels from 0.5% to 12%, preferably from 1.5% to 5%. It can be made solid and semi-solid viscous with 1.5% ink and without perfume. Examples of suitable dyes are light blue Alizarin (C.1.63010), blue letter VP (C.l. 24401), acid green 2G (C.I.42085, green Astrogen D (C.I. 42040, Cyanine of supranol 7B (.1. 42675, blue 3 RL Maxilon (C. blue 80 basic), blue Drimarino Z-RL (blue C. reactive 18), light blue Alizarin H-RL (acid blue 182), blue No. 1 FD &C and green No. 3 FD &C.

(See Kitko patents, U.S. Patent No. 4,248,827 omitted on February 3, 1981 and U.S. Patent No. 4,200,606, issued April 29, 1980, both incorporated herein by reference) C.l. it refers to the color index.

Additional Auxiliary Ingredients. As a preferred embodiment, the conventional auxiliary ingredients that are employed in this invention may be chosen from the typical components such as enzymes (compatible with that applicable with other auxiliary ingredients), especially proteases, lipases, cellulases, color spots, foam enhancers, foam suppressors, anti-rust and / or anti-corrosive agents, stain-suspending agents, germicides, alkalinity sources, hydrothores, antioxidants, enzyme stabilizing agents, solvents, clay stain chelating agents will generally consist of about 0.1% 10% by weight of the detergent compositions herein. Most preferably, thus it is used, the chelating agents will consist of about 0.15 to about 3.0% by weight of such agents of removal / anti-redeposition compositions, polymeric dispersing agents, transfer inhibiting agents, etc. dye, including polyamine N-oxides such as N-vinylimidazole and N-vinylpyrrolidone, etc.

EXAMPLE 1 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 grit (1.56 g, 224. 5 mmoles). The solution is refluxed for 6 hours under argon, diluted with 500 ml of methanol and allowed to crystallize in the cold at 0 ° C for 18 hours. The resulting green solid is collected by filtration, dried in vacuo 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-butoxyphthalonyl trile.

EXAMPLE 2 Preparation of naphthalocyanine To a solution of dilithium naphthalocyanine (2 g, 2.75 mmol) in DMF (200 ml) is added 1 N HCl (10 ml). The solution is stirred at temperature environment for 1 hour. The solution is diluted with 200 ml of water for approximately 30 minutes. The resulting green solid is collected by filtration, dried in vacuo 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, 31H-phthalocyanine; 2, 3, 9, 10, 16, 17, 23, 24-octachloro-29H, 31 H-phthalocyanine; and tetrabutoxy-29H, 31 H-phthalocyanine.

EXAMPLE 3 Preparation of tin naphthalocyanine dichloride (IV) A mixture of naphthalocyanine (0.2 g, 0.28 mmole), tin tetrachloride pentahydrate (0.456 g, 1.3 mmole) in DMF is refluxed for one hour under argon and then treated. Allow it to cool. The resulting green solid is filtered, dried under vacuum, and used without further purification. The above process is suitable for preparing tin phthalocyanine dichloride 1, 4,8, 11, 15, 18,22,25-octabutoxy tin (IV); tin phthalocyanine dichloride 2,3,9,10,16,17,23,24-octachloro (IV); and tin tetrabutoxy phthalocyanine dichloride (IV).

EXAMPLE 4 Preparation of germanium naphthalocyanine dichloride (IV) To a refluxed solution of naphthalocyanine (0.20 g, 0.28 mmol), germanium tetrachloride (0.15 ml) in anhydrous DMF (20 ml) under argon, additional 0.5% tetrachloride (0.25 ml) is added in portions over a period of 5 hours. ). The solution is cooled, diluted with 940 ml dichloromethane, extracted twice with 30 ml portions of 10% hydrochloric acid, then three times with 30 ml portions of distilled water, dried over MgSO4, filtered and concentrated to produce a green solid that is used without further purification. The above process is suitable for the preparation of phthalocyanine dichloride 1, 4,8,11, 15,18,22,25-octabutoxy germanium (IV); phthalocyanine dichloride 2,3,9,10,16,17,23,24-octachlor germanium (IV); and phthalocyanine germanium tetrabutoxy dichloride (IV).

EXAMPLE 5 Preparation of 1, 4,8,11,15,18,22,25-octabutoxy platinum (IV) dichloride To a refluxing solution of 1, 4,8,11, 15,18,22,25-octabutoxyphthalocyanine (0.20 g, 0.18 mmol), platinum tetrachloride (0.15 ml) in 20 ml of anhydrous N, low N-dimethylformamide Argon over a period of 5 hours platinum tetrachloride (0.25 ml) is added in a circus. The The solution is cooled, diluted with 40 ml of dichloromethane, 2x30 ml is extracted % hydrochloric acid, 3x30 ml distilled water, dried over anhydrous magnesium sulfate and removed from the solvent to produce a green solid that is used without further purification.

EXAMPLE 6 Preparation of 1, 4,8,11,15,18,22,25-octabutoxy phthalocyanine germanium (IV) di- (polyethylene glycol 350) methyl ether A mixture of phthalocyanine dihydroxide 1, 4.8, 11, 15, 18,22,25-octabutoxy of germanium (IV) (1.0 g, 0.81 mmol), methyl ether poly (ethylene glycol 350) (22.68 g, 64.8 mmol) and xylene (175 ml) heat slowly under reflux under argon for a period of 3 hours. The reaction flask is fitted with a Dean-Stark tape and the water is removed by azeotropic distillation. After 48 hours the reaction is cooled, the solvent is removed in vacuo and the crude product is used without further purification. The above process is suitable for use in the preparation of 1, 4,8,11, 15,18,22,25-octabutoxy phthalocyanine germanium (IV) di- (glycerol-di- (diethylene glycol)) methyl ether; 1, 4,8,11, 15,18,22,25-octabutoxy phthalocyanine germanium (IV) di- (Neodol 23-6.5); tin tetrabutoxy phthalocyanine (IV) di- (poly (ethylene glycol 350) methyl ether); tetrabutoxy phthalocyanine tin (IV) methyl ether di- (glycerol-di- (diethylene glycol)); and tin tetrabutoxy phthalocyanine (IV) di- (Neodol 23-6.5).

EXAMPLE 7 Preparation of 1,48,11,15,18,22,25-octabutoxy of phthalocyanine germanium (IV) of -di- (dimethyl sulfate triethanolamine quaternary) A mixture of 1, 4,8,11, 15, 18,22,25-octabutoxy phthalocyanine dihydroxide germanium (IV) (0.5 g, 0.405 mmol), anhydrous triethanolamine (10 g, 67.04 mmol) and xylene (175 ml ) is heated slowly to reflux for a period of 1.5 hours. The reaction flask is fitted with a Dean-Stark trap and the water is removed by azeotropic distillation. After 2 hours the solution is cooled, and the solvent is removed in vacuo. The resulting oil is dissolved in 50 ml DMF and slowly added to 800 ml of water over a period of 0.5 hours. The resulting blue solid is collected by filtration and dried under vacuum at 80 ° C. This solid product is added to dioxane (100 ml) containing dimethyl sulfate (0.15 g., 1,215 mmoles). The resulting blue solid is collected by filtration, dried and used without further purification. The above process is suitable for use in the preparation of tin (IV) phthalocyanine tetrabutoxy-di-dimethylsulfate (quaternary triethanolamine).

The cleaning compositions provided according to this invention may be in the form of granules, liquids, sticks and the like, and are typically formulated to provide a pH in use in the range of 9 to 11, however, in the case of non-aqueous compositions or of low aqueousness the pH ranges may vary outside this range. Various carriers such as sodium sulfate, water, water-ethanol, BPP, MPP, EPP, PPP, sodium carbonate, and the like, can be used routinely to formulate the finished products. Granules can be produced by spray drying or by agglomeration as by known techniques, to provide products in the density range of 150-950 g / l. The bars can be formulated using conventional extrusion techniques. The photobleaching chelator may be preformed with more gas if desired. The compositions may also contain conventional perfumes, bactericides, hydrotropes and the like. In the case of non-aqueous or low water-borne compositions, the cleaning compositions can be applied to an article that is used to deliver the compositions of the present invention to a fabric or a hard surface. Non-limiting examples of the compositions according to this invention are as shown below: EXAMPLES 8-11% in Weight 1. Dirt releasing agent in accordance with the patent E.U.A. 4,968,451, Scheibel et al. 2. Di-poly (ethylene glycol 350) deoctabutoxy phthalocyanine germanium (IV) photobenzalizer according to Example 6. 3.-Photolanter of poly (ethylene glycol 350) tin octabutoxiftalocyanine (IV) according to example 6.

EXAMPLES 12-15 1. - Ethylenediamine tetramethylene phosphonate. 2.- Dirt releasing polymer according to the Patent of E.U.A. 5,415,807, Gosselink et al., Issued May 16, 1995. 3. - Dirt release polymer according to the Patent E.U.A. 4,792,857, Goseelink issued October 27, 1987. 4.- Dispersant of hydrophobic dirt according to the patent E.U.A. 5,565,145, Watson et al. Issued October 15, 1996. 5.- Photobutadiene octabutoxiftalocianina of germanium (IV) according to example 7. 6.- Photobutanol tetrabutoxiftalocianina tin (IV) according to example 7.

EXAMPLE 16 Ingredients% in Weight 1. - Photobleach according to example 12.

EXAMPLE 17 Lightly aqueous cleaning composition Ingredients Weight% 1. - Octabutoxiftalocianina octabotoxin of di [glycerol-di- (diethylene glycol methyl ether)] germanium (IV). 2. Other co-solvents that may be used herein in conjunction with major solvents BPP, MPP, EPP and PPP including various glycol ethers, including materials marketed under the trademarks of Carbitol, Carbitol methyl, butyl Carbitol, Carbitol propyl, hexyl Cellosolve, and the like . If desired, and with due consideration for safety and odors for domestic use, several conventional chlorinated solvents and hydrocarbon solvents can be used to dry cleaner. Including among these 1,2-dichloroethane, trichlorethylene, isoparaffins, and mixtures thereof. 3.- As described in the Patents of E.U.A. 4,758,641 and ,004,557, said polyacrylates include homopolymers that can crosslink in varying degrees, as well as non-crosslinked ones. What is preferred here are homopolymers having a molecular weight in the range of from about 100,000 to about 10,000,000, preferably 2,000,000 to 5,000,000. For the materials described in Example 29, excellent cleaning performance is ensured using any non-immersion process and articles to provide from about 5 g to about 50 g of the cleaning compositions per kilogram of fabric to be cleaned. The use of polyacrylate emulsifiers at low levels minimizes waste in fabrics. The fabrics are washed using the above compositions, typically at use concentrations of about 10 ppm to about 10,000 ppm. The fabrics are dried in the presence of light, preferably natural sunlight, to achieve improved photobleaching benefits.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - An oxygen generator in photochemical singlet having a wavelength of maximum absorption of Q band of 660 nanometers or greater, having the formula: or the formula: Further characterized in that M is a metal or non-photoactive metal, said metal or non-metal chosen from the group consisting of Sn, Ge, Pt, Pd, Pb, P and mixtures thereof; the units R, R2, R3, R4, R5, and R6 are independently selected from the group consisting of: a) hydrogen, b) halogen, c) hydroxyl; d) C1-C22 alkyl, branched C3-C22 alkyl, C-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof, e) C1-C22 alkyl substituted by halogen, branched C3-C22 alkyl , C2-C22 alkenyl. C3-C22 branched alkenyl, or mixtures thereof, f) C3-C2 alkyl substituted by polyhydroxyl; g) C1-C22 alkoxy; h) branched alkoxy having the formula: wherein Z is hydrogen, hydroxyl, CrC3o alkyl, C? -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 and independently has the value from 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 alkylenearyl or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl or mixtures thereof; m) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl, or mixtures thereof; n) thioalkyl of C? -C22, branched C3-C22 thioalkyl, 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 O3-C22 alkenyl, or mixtures thereof, ii) C1-C22 alkyl substituted with halogen; branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; Ii) C3. C22 alkylene substituted by polyhydroxyl, 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 alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of the formula: wherein R 10 and R 11 are C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 anynyl, branched C 3 -C 22 alkenyl, or mixtures thereof; R12 is i) hydrogen, ii) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 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 wherein R17 and R18 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit of the formula: (A) v (CH2) and (OCH2CH2) xZ where Z is: i) hydrogen, ii) hydroxyl, ii) -CO2H, v) -SO3"M +, v) -OSO3" M +, vi) alkoxy of Ci-Cß, vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; ix) alkyleneamino 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: -OSR19R20R21, wherein each R19, R20 and R21 is independently i) C1-C22 alkyl, C3-C22 alkyl branched, 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: (A) v (CH2) and (OCH2CH2) x Z wherein Z is: a) hydrogen, b) hydroxyl, c) -CO2H; d) -SO3"M +, e) -OSO3" M +, f) CrC6 alkoxy; g) substituted aryl, non-substituted ary, or mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; i) alkyleneamines 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; axial units R wherein each R is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C 1 -C 22 alkyl, branched C 3 -C 22 alkyl, C 2 -C 22 alkenyl. C3-C22 branched alkenyl, or mixtures thereof, e) C1-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, C3_3alkyl, 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 having the value from 0 to 100, i) substituted aryl, unsubstituted aryl or mixtures thereof, j) substituted alkylenearyl, non-aikaryl aryl substituted or mixtures thereof: k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof, I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl or mixtures thereof, m) substituted alkylenediaryl and unsubstituted alkylenediaryl, or mixtures thereof; n) thioalkyl C1-C22, branched C3-C22 thioalkyl, or mixtures thereof: o) a carboxylate of the formula O-O-C-R9 wherein R9 is i) C1-C22 alkyl. branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof ii) C1-C22 alkyl substituted with halogen; branched C3-C22 alkyl, C-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; iii) C3. C22 alkylene substituted by polyhydroxyl; v) C3-C22 glycol; v) C1-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 alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit with the formula: wherein R10 and R11 are C22alkyl, branched C3-C22alkyl, C2-C22alkenyl, branched C3-C22alkenyl, or mixtures thereof R12 is i) hydrogen, ii) C1-C22alkyl, 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 C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit of the formula: (A) v (CH2) and (OCH2CH2) x Z where Z is: i) hydrogen, ii) hydroxyl, ii) -CO2H, iv) -SO3"M \ v) -OSO3" M +, vi) alkoxy of C? -C6, 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 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: -OSR19R20R21, 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; ü) substituted aryl, unsubstituted aryl, 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) CI-CT 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 cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12, or mixtures thereof; 2. A laundry or cleaning composition consisting of: A) At least about 0.1%, preferably from about 0.1% to about 30%, most preferably from about 1% to about 30%, very much 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, zwitterionic nonionic, ampholytic surfactants and mixtures thereof; B) at least about 0.001 ppm, preferably about 0.01 about 10000 ppm, most preferably about 0.01 about 5000 ppm, most preferably about 10 about 1000 ppm, of a compound photosensitizer that has a wavelength of maximum absorption of Q band of 660 nanometers or greater that has the formula: or that have the formula: Characterized further because M is Sn, Ge, Pt, Pd, Pb, P and mixtures thereof; where the units R1, R2, R3, R4, R5, and R6 each are chosen independently of the group consisting of: where M is a metal or non-photoactive metal, said metal or non-metal chosen from the group consisting of Sn, Ge, Pt, Pd, Pb, P and mixtures thereof; the units R1, R2, R3, R4, R5, and R6 each independently are selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C1-C22 alkyl, branched C3-C2 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof e) C1-C22 alkyl substituted by halogen, branched C3-C22 alkyl , C2-C22 alkenyl, branched C3-C22 ainnyl, or mixtures thereof, f) C3-C22 alkyl substituted by polyhydroxyl; g) C22 C alkoxy; h) branched alkoxy having the formula: OR wherein Z is hydrogen, hydroxyl, C? -C30 alkyl > C? -C30 alkoxy, -CO2H, -OCH2CO2H, -SO3"M +, -OSO3" M +, -PO32"M, -OPO32-M or mixtures thereof; M is a water-soluble cation in an amount sufficient to satisfy load equilibrium, x is 0 or 1, each y independently has the value from 0 to 6, each z has independently the value from 0 to 100, i) substituted aryl, unsubstituted aryl or mixtures thereof; substituted alkylenearyl, unsubstituted alkylenearyl or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; I) substituted oxyalkylene aryl, unsubstituted oxyalkylenearyl or mixtures thereof; m) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl, or mixtures thereof; n) thioalkyl of C C22 > branched C3-C22 thioalkyl, 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 i) C1-C22 alkyl substituted with halogen; branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; iii) C3. C22 alkylene substituted by polyhydroxyl, iv) C3-C22 glycol; v) C1-C22 alkoxy, vi) branched C3-C2 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 C-1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; R12 is i) hydrogen, i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 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 wherein R17 and R18 are C? -C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyleneoxy unit of the formula: (A (CH2) and (OCH2CH2) x Z where Z is: i) hydrogen, i) hydroxyl, iii) -CO2H, iv) -SO3"M +, v) -OSO3" M +, vi) alkoxy of Ci- Cβ, vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; ix) alkyleneamino 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) C?-C22 alkyl > branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof, ii) substituted aryl, unsubstituted aryl, or mixtures thereof; iü) 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) CrC6 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 cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12, and mixtures thereof; axial units R wherein each R is independently selected from the group consisting of: a) hydrogen; b) halogen; c) hydroxyl; d) C 1 -C 22 alkyl, branched C 3 -C 2 alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof e) C 1 -C 22 alkyl substituted by halogen, C 3 -C 22 alkyl branched, 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: CH2- (0)? (CH2) and (OCH2CH2) z -Z -O-CH CH2- (0)? (CH2) and (OCH2CH2) z -Z wherein Z is hydrogen, hydroxyl, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, -CO 2 H, -OCH 2 CO

2 H, -SO 3"M +, -OSO 3 'M" -PO 32"M, -OPO 32" M or mixtures thereof; M is a cation soluble in water in an amount sufficient to satisfy the balance of the load; 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 alkylenearyl or mixtures thereof; k) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; I) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl or mixtures thereof; m) substituted alkyleneoxyaryl and unsubstituted aiylenoxyaryl, or mixtures thereof; n) C1-C22 thioalkyl, branched C3-C22 thioalkyl, or mixtures thereof; o) a carboxylate of the formula: O-OC-R9 wherein R9 is: i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof ii) C1-C22 alkyl substituted with halogen; branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; iii) C3. C22 alkylene substituted by polyhydroxyl; v) C3-C22 glycol; v) C1-C22 alkoxy, vi) branched C3-C22 alkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof; viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; X) 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 with the formula: wherein R 0 and R 11 are 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 R 12 is i) hydrogen, ii) C 1 -C 8 alkyl C22, branched C3-C22 alkyl, C2-C22 alkenyl. C3-C22 branched 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 C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl or mixtures thereof; r) an alkylethyloxy unit of the formula: (A) v (CH2) and (OCH2CH2) xZ wherein Z is: i) hydrogen, ii) hydroxyl, iii) -CO2H, iv) -SO3"M +, v) -OSO3"M +, vi) C? -C6 alkoxy, vii) substituted aryl, unsubstituted aryl, or alkyleneamino mixtures or mixtures thereof; A is nitrogen or oxygen; M is one these; viii) substituted aryloxy, unsubstituted aryloxy or mixtures thereof; ix) water-soluble cation; 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, 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: (A) v (CH2) and (OCH2CH2)? Z 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 cation soluble in water; v is 0 or 1; x is from 0 to 100, and is from 0 to 12, or mixtures thereof; C) the rest of the vehicle and auxiliary ingredients.

3. A composition according to any of claims 1 or 2 further characterized in that the photosensitizing compound consists of units R1, R2, R3, R4, R5, and R6 independently chosen from the group consisting of hydrogen, hydroxyl, halogen, thioalkyl of C1-C22, branched C3-C22 thioalkyl, C1-C22 alkoxy, branched C3-C22 alkoxy, aryloxy, an alkylethyleneneoxy unit of the formula: - (A) v- (CH2) and (OCH2CH2) ΔZ characterized in addition because Z consists of hydrogen, hydroxyl, -CO2H, -SO3"M +, -OSO3" M +, CrC6 alkoxy, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy, alkyleneamino; and mixtures of these; A consists of nitrogen or oxygen, M is a water-soluble cation, v is 0 or 1, x is 0 to 100, and is from 0 to 12.

4. A composition according to any of claims 1 to 3, further characterized in that the axial R units consist of: a) alkylethynesoxy units of the formula ___ (A) v - (CH2) and (OCH2CH2) xZ further characterized because Z consists of hydrogen, hydroxyl, -C02H, -SO3" M +, -OS? 3"M +, C? -C6 alkoxy, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy, alkylene amino; A consists of nitrogen or oxygen, M is water soluble cation, v is 0 or 1, x is from 0 to 100, and is from 0 to 12; b) branched alkoxy of the formula CH2- (O)? (CH2) and (OCH2CH2) z -B -O- CH CH2 - (O)? (CH2) and (OCH2CH2) z - B further characterized in that B is hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkoxy, -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 from 0 to 6, each z independently has the value from 0 to 100; c) substituted siloxy of the formula -OsR7R8R9 further characterized in that each R7, R8 and R9 are independently selected from the group consisting of C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, C3 alkenyl Branched C22, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy, an alkylethyleneoxy unit of the formula ~ (A) v- (CH2) and (OCH2CH2) ZZ further characterized in that Z consists of hydrogen, alkyl of C? -C30, hydroxyl, -CO2H, -SO3"M +, -OSO3" M +, C? -C6 alkoxy, substituted and unsubstituted aryl, substituted and unsubstituted aryloxy, alkyleneamino, and 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; preferably branched alkoxy with the formula: CH2- (O)? (CH2) and (OCH2CH2) z -B-O- CH CH2o- ((O)? (CH2) and (OCH2CH2) z -B further characterized in that B is hydrogen, hydroxyl, C -? - C3o alkyl, C1-C30 alkoxy, -CO2H, -CH2CO2H, -SO3"M +, -OSO3" M +, -PO32"M, OPO32" M, and mixtures of these, M is a cation soluble in water in an amount sufficient 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.

5. A composition according to any of claims 1 to 4, further characterized because the auxiliary ingredients are members chosen from the group consisting of pH regulators, detergency builders, chelating agents, filler salts, soil release dispersing agents, enzymes, enzyme promoters, perfumes, thickeners, solvents, clays, bleaches, and mixtures of these .

6. A laundry or cleaning composition comprising: A) at least 0.1%, preferably from 0.1% to 30%, most preferably from 1% to 30%, very much preferably from 5% to 20% by 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 0.001 ppm, preferably from 0.01 to 10000 ppm, most preferably from 0.1 to 5000 ppm, very much preferably from 10 to 1000 ppm, of a photosensitizing compound having a maximum absorption wavelength of the Q band of 660 nanometers or higher that has the formula: or that has the formula: further characterized in that M is a metal or non-photoactive metal selected from the group consisting of Sn, Ge, Pt, Pd, Pb, P, and mixtures thereof; the units R1, R2, R3, R4, R5, and R6 are portions that provide a positive field Dtriplete of at least 1, preferably at least 10, most preferably at least 30, when said portion replaces hydrogen; further characterized in that the R units are axial units, said R units independently are chosen from the group consisting of: a) hydrogen; b) halogen; c) hydroxy; d) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 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) C1-C22 alkoxy; h) branched alkoxy having the formula: further characterized in that Z is hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkoxy, -CO2H, -OCH2CO2H, -SO3"M +, -OS03" M +, -P032"M, OPO32" M or 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; i) substituted aryl, non-substituted ary, or mixtures thereof; j) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k) aryloxy substituted, 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; o) a carboxylate of the formula: O-O-C-R9 further characterized in that R9 is: i) C1-C22 alkyl. C3-C22 branched alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; I) C1-C22 alkyl substituted with halogen, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; Ii) C3-C22 alkylene substituted with polyhydroxyl; iv) glycol of Q3-C22; v) C1-C22 alkoxy; vi) branched C3-C22 alkoxy; v¡¡) 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: further characterized in that R 10 and R 11 are C 1 -C 22 alkyl, C 3 -C 22 branched alkyl, C 2 -C 22 alkenyl, branched C 3 -C 22 alkenyl, or mixtures thereof; R12 is i) hydrogen; ii) C-C22 alkyl, branched alkyl of C3-C22, C2-C22 alkenyl, branched C3-C22 alkenyl, 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 further characterized in that R17 and R8 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; r) an alkylethyloxy unit of the formula: ... (A) v- (CH2) and (OCH2CH2) Z wherein Z is: i) hydrogen, ii) hydroxyl, ii) -CO2H, iv) -SO3"M + , v) -OSO3"M +, vi) Ci-Cβ 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 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: -OSR19R20R21, 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; ü) substituted aryl, unsubstituted aryl, 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; ) Alkyleneamines 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, or mixtures thereof; and B) the rest of the vehicle and auxiliary ingredients.

7.- A composition for laundry or cleaning that consists of: A) at least 0.1%, preferably from 0.1% to 30%, most preferably from 1% to 30%, very much preferably from 5 to 20% by weight, of a detersive surfactant, said detersive surfactant is selected from the group which comprises anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; B) at least 0.001 ppm, preferably from 0.01 to 10000 ppm, most preferably from 0.1 to 5000 ppm, very much preferably from 10 to 1000 ppm, of a photosensitizing compound having a maximum absorption wavelength of the Q band of 660 nanometers or higher that has the formula: or that has the formula: further characterized in that M is a metal or non-photoactive metal selected from the group consisting of Sn, Ge, Pt, Pd, Pb, P, and mixtures thereof; the units R1, R2, R3, R4, R5, and R6 are portions that provide a positive value of change to red of at least 1, preferably a positive change to red value of at least 10, most preferably a positive change to red value of at least 30, when said portions are replaced by hydrogen; the R units are axial units, said R units independently are chosen from the group consisting of: a) hydrogen; b) halogen; c) hydroxy; d) C1-C22 alkyl. C3-C22 branched alkyl, C2-C22 alkenyl, branched C3-C22 alkenii, or mixtures thereof; e) C1-C22 alkyl substituted with halogen, branched C3-C22 alkyl, C2-C22 alkenyl. branched C3-C22 aikenyl, or mixtures thereof; f) C3-C22 alkyl substituted with polyhydroxyl; g) C1-C22 alkoxy; h) branched alkoxy having the formula: further characterized in that the Z is hydrogen hydroxyl, C? -C30 alkyl, C30 alkoxy, -CO2H, -OCH2CO2H, -SO3-M +, -OSO3"M +, -PO32" M, -OPO32"M, or mixtures of these, 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 0 to 100; substituted aryl, unsubstituted aryl, or mixtures thereof; j) substituted alkylenearyl, unsubstituted alkylenearyl, 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; o) a carboxylate of the formula: further characterized in that R9 is: i) C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl. C3-C22 branched alkenyl, or mixtures thereof; ii) C1-C22 alkyl substituted with allogen, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; iii) C3-C22 alkylene substituted with polydroxyl; iv) C3-C22 glycol; v) C1-C22 alkoxy; vi) branched C3-C22 alkoxy; vii) substituted aryl, unsubstituted aryl or mixtures thereof; viii) substituted alkylenyl, unsubstituted alkylenyl, or mixture thereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x) substituted oxyalkylenearyls, unsubstituted oxyalkylenearyls, mixtures thereof; xi) substituted oxyalkylene oxide, unsubstituted oxyalkylene oxide, mixtures thereof; p) an alkyleneamine unit of the formula: further characterized in that R 0 and R 11 are 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; 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 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 further characterized in that R17 and R19 are C1-C22 alkyl, branched C3-C22 alkyl, C2-C22 alkenyl, branched C3-C22 alkenyl, or mixtures thereof; r) an alkylethyleneoxy unit of the formula: - (A) v- (CH 2) y (OCH 2 CH 2) σ Z further characterized in that Z is: i) hydrogen; ii) hydroxyl; iii) -CO2H; iv) -S? 3"M +; v) -OSO3" M +; vi) Ci-Cß 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 from 0 to 12; s) substituted siloxy of the formula: -OSR19R20R21 further characterized in that each R19, R20, and R21 is independently i) C? -C22 alkyl > C3-C22 branched alkyl, C2-C22 alkenyl, branched C3-C22 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: - (A) v- (CH2) and (OCH2CH2)? Z further characterized in that 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) 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; and B) the rest of the vehicle and auxiliary ingredients.

8. A method for cleaning a hard surface consisting of making contact with a hard surface when it needs to be cleaned with an aqueous cleaning composition consisting of 0.001 ppm of a photosensitizing compound according to any one of the claims of 1 to 6 and exposing the hard surface to a light source that has a minimum wavelength range of 300 to 1200 nanometers.

9. A method for cleaning a fabric stained with a cleaning material consisting of an aqueous cleaning composition that consists of contacting the stained fabric in need of stain removal with a slightly aqueous cleaning solution consisting of less than 50% water and at least 0.001 ppm of the photobleaching compound according to any of claims 1-6 followed by exposure of the treated surface of the fabric to a light source having a minimum wavelength scale of 300 to 1200 nanometers.

10. - A method for cleaning a hard surface with a low water cleaning composition that consists in contacting the hard surface when it needs to be cleaned with a low water cleaning composition consisting of less than 50% water and at least 0.001 ppm a photosensitizing compound according to any of claims 1 to 6, and exposing the hard surface to a light source having a minimum wavelength range of 300 to 1200 nanometers.

11. A bleaching composition consisting of: a) at least 0.01% of a non-hypoaltytic bleach; b) at least 0.001 ppm, preferably 0.1 to 10000 ppm, most preferably 0.1 to 500 ppm, most preferably 10 to 100 ppm, of a photosensitizing compound having a maximum absorption wavelength of Q of 660 nanometers or greater according to claim 1; and e) the remaining vehicles and auxiliary ingredients, preferably blasting activators.

12. A composition according to claim 11, further characterized in that the non-hypoaltytic bleach is selected from the group consisting of percaboxylic acids, peroxides, percabonates, perborates and mixtures thereof.