USOO641715OB2 (12) United States Patent (10) Patent No.: US 6,417,150 B2 Willey (45) Date of Patent: *Jul. 9, 2002

(54) LOW HUE PHOTOBLEACHES OTHER PUBLICATIONS (75) Inventor: Alan David Willey, Cincinnati, OH Brasseur, N., et al., “Synthesis and Photodynamic Activities (US) of Silicon 2,3-Naphthalocyanine Derivatives”, J. Med. Chem., vol. 37, p. 415-420 (1994). (73) Assignee: Case Western Reserve University, Chan, W.S., et al., “Photosensitising Activity of Phthalocya Cleveland, OH (US) nine Dyes Screened Against Tissue Culture Cells', Angew Photochemistry & Photobiology, vol. 45, No. 6, pp. 757-761 (*) Notice: This patent issued on a continued pros (1987). ecution application filed under 37 CFR Cook, M.J. et al., “Octa-alkoxy Phthalocyanine and Naph 1.53(d), and is subject to the twenty year thalocyanine Dertivatives: Dyes with Q-band Absorption in patent term provisions of 35 U.S.C. the Far Red or Near Infrared' J. Chem. Soc., Perkin Trans., 154(a)(2). vol. I., p. 2453–2458 (1988). Subject to any disclaimer, the term of this Dirk, C.W., et al., “Cofacial Assembly of Partially Oxidized patent is extended or adjusted under 35 Metallomacrocycles as an Approach to Controlling Lattice U.S.C. 154(b) by 0 days. Architecture in Low-Dimensional Molecular Solids. Chemical and Architectural Properties of the “Face-toFace” This patent is Subject to a terminal dis Polymers M(phthalocyaninato)OWhere M= Si, Ge, and claimer. Sn”, J. Am. Chem. Soc., vol. 105, pp. 1539–1550 (1983). Esposito, J.N. et al., “The Synthesis and Physical Properties (21) Appl. No.: 09/355,154 of Some Organo- and Organosiloxysilicon Phthalocya (22) PCT Filed: Jan. 22, 1998 nines”, Inorg. Chem., vol. 5, No. 11, pp. 1979-1984 (Nov. 1966). (86) PCT No.: PCT/US98/00225 Ford, W.E. et al., “Synthesis and Photochemical Properties S371 (c)(1), of Aluminum, Gallium, Silicon, an Tin Naphthalocyanines”, (2), (4) Date: Jul. 23, 1999 Inorg. Chem., vol. 31, p. 3371-3377 (1992). Hayashida, S., et al., “Effect of Axial Substituents on the (87) PCT Pub. No.: WO98/32832 Aggregate of Silicon Naphthalocyanine in the Vacuum PCT Pub. Date:Jul. 30, 1998 Deposited Thin Films”, Chem. Lett., pp. 2137–2140 (1990). Joyner, R.D. et al., “Phthalocyaninosilicon Compounds', Related U.S. Application Data Inorg. Chem., vol. 1, No. 2, pp. 236-238 (May 1962). (60) Provisional application No. 60/035,903, filed on Jan. 24, Kato, S., et al., “Preparation of a New Series of Trinuclear 1997. Metallophthalocyanines and -porphyrins, Angew. Chem. Int. Ed. Engl., vol. 18, No. 1, pp. 82-83 (a879). (51) Int. Cl...... C11D 7/22 Kraut, B., et al., “Photochemical Properties of Tin(IV) Phthalocyanines: a Comparison between the Dichloro and (52) U.S. Cl...... 510/301 Superphthalocyanines”, Inorganica Chimica Acta, Vol. 149, pp. 273–277 (1988). (58) Field of Search ...... 510/301,367 Kroenke, W.E. et al., “A Series of Phthalocyaninotin Com (56) References Cited plexes”, Inorg. Chem., vol. 3, No. 2, pp. 251-254 (Feb. U.S. PATENT DOCUMENTS 1964). 3,094,536 A 6/1963 Kenney et al...... 260/314.5 (List continued on next page.) 3,927,967 A 12/1975 Speakman ...... 8/103 4,033,718 A 7/1977 Holcombe et al...... 8/103 Primary Examiner John Hardee 4,166,718 A 9/1979 Reinert et al...... 8/111 (74) Attorney, Agent, or Firm-Fay, Sharpe, Fagan, 4,240,920 A 12/1980 de Luque ...... 252/99 Minnich & McKee, LLP 4.255.273 A 3/1981 Sakkab ...... 252/102 4,256,597 A 3/1981 Sakkab ...... 252/99 (57) ABSTRACT 4,318,883 A 3/1982 Polony et al...... 422/22 4,368,053 A 1/1983 Eckhardt et al...... 8/102 Low hue photobleaching compositions comprising organo 4,497,741 A 2/1985 Hölzle et al...... 260/245.77 tin (IV), organogermanium(IV), organoplatinum (IV), orga 4,648,992 A 3/1987 Graf et al...... 540/124 nopalladium (IV), organolead (IV) or organophosphorous 5,916,481. A * 6/1999 Willey ...... 252/186.21 (III) phthalocyanine and naphthalocyanines having Q-band absorption maxima at wavelengths greater than 660 nm and FOREIGN PATENT DOCUMENTS increased triplet State yields whereby production of Singlet EP O 285965 10/1988 ...... CO9B/67/22 oxygen is increased. Use of Sn, Ge", Pt', Pd, Pb, Pt EP O381,211 8/1990 ... G11B/7/24 phthalocyanine and naphthalocyanines compounds in pho EP O 484O27 5/1992 ...... CO9B/47/04 tobleaching compositions allows for formulation of low hue GB 1372035 10/1974 laundry compositions, bleach compositions, and hard Sur GB 1408144 1/1975 face cleaners. GB 2159516 12/1985 ...... CO9B/47/04 JP 6-73397 3/1994 ...... C11D/3/395 WO WO 91/18006 11/1991 ...... CO7J/43/OO 20 Claims, No Drawings US 6,417,150 B2 Page 2

Kroenke, W.E. et al., “The Infrared Spectra of Some Tin and Soncin, M., et al., “Effect of the Delivery System on the Lead Phthalocyanines”, Inorg. Chem., vol. 3, No. 5, pp. Biodistribution of Ge(IV) octabutoxy-phthalocyanines in 696–698 (May 1964). Lowery, M.H. et al., “Dichloro(phthalocyanino)silicon", Tumour-bearing Mice', Cancer Letters, vol. 89, pp. Inorg. Chem., vol. 4, p. 128 (1965). 101-106 (1995). Moyer, T. J., et al., “Iodine Doped (SiNcO). A new Wen, T-C., et al., “Synthesis and Photoproperties of Silicon Conducting Polymer', Polymer Preps, vol. 25, p. 234-235 Phthalocyanines and Silicon Naphthalocyanines”, J. Chin. (1986). Nyokong, T., “Photoreduction of Tin(IV) Phthalocyanines”, Chem. Soc., vol. 40, pp. 141-147 (1993). Polyhedron, vol. 13, No. 13, pp. 2067-2071 (1994). Wheeler, B.L. et al., “A Silicon Phthalocyanine and a Silicon Rafaeloff, R., et al., “New Group IV Phthalocyanines”, J. Naphthalocyanine, Synthesis, Electrochemistry, and Elec Inorg. Nucl. Chem., vol. 28, pp. 899–902 (1966). Rihter, B.D., “Synthesis and Photoproperties of Diamag trogenerated Chemiluminescence', J. Am. Chem. Soc., Vol. netic Octabutoxyphthalocyanines with Deep Red Optical 106, p. 7404–7410 (1984). Absorbance”, J. Am. Chem. Soc., vol. 112, pp. 8064-8070 Witkiewic, Z. et al., “Properties of Octamethoxyphthalocya (1990). Sayer, P., “Metalloid Porphyrins and Phthalocyanines”, Acc. nines I. On their Syntheses, electrical conductivity, and Chem. Res., vol. 15, pp. 73–79 (1982). catalytic activity, Material Science, Vol. 11, No. 1-2, pp. Snow, A. W., “Molecular Associattion and Monolayer For 39-45 (1976). mation of Soluble Phthalocyanine Compounds”, J. Am. Chem. Soc., vol. 106, pp. 4706–4711 (1984). * cited by examiner US 6,417,150 B2 1 2 LOW HUE PHOTOBLEACHES A further task for the formulators of photobleaches has been the need to modify the properties of the photoSensitizer This claims priority to U.S. Provisional Application (Sens.) unit of the molecule, in other words, to increase the 60/035,903, filed Jan. 24, 1997. quantum efficiency without reducing the water Solubility. While balancing water solubility and enhanced photophys FIELD OF THE INVENTION ics. the formulator must insure that the Structural modifica tions do not increase the color. The present invention relates to novel organotin, It is well known to formulators skilled in the art that an R organogermanium, organoplatinum, organopalladium, unit which may produce a desired increase in one of these organolead, or organophosphorous photoSensitizing com three properties may cause an equally large decrease in one pounds having a Q-band maximum absorption wavelength or both of the other desirable properties. of 660 nanometers or greater and their use as photoactivators Surprisingly, it has been found that the compounds of the (photosensitizer) or Singlet oxygen producers, in particular present invention allow the formulators to modify the levels for low hue photobleaching for removing Stains from textiles of Solubility, photoefficiency, Q-band wavelength maxima and hard Surfaces. The present invention also relates to 15 Separately without adversely affecting the other parameters laundry compositions and hard Surface cleaners comprising of the molecule. This ability to delineate and selectively the novel organotin, organogermanium, organoplatinum, modify the key Structural elements contributing to the target organopalladium, organolead, or organophosphorous photo properties of the molecule allows the formulator to proceed Sensitizing compounds of the present invention. The present without having to rely upon a "hit and miss Stratagem. invention further relates to a method of delivering compo The photobleaches of the invention comprise two “ele Sitions comprising low hue photobleaches to Soiled and ments'. The photoSensitizing ring which is optimized for Stained fabrics and to hard Surfaces. color (hue) and generation of Singlet oxygen, and axial groups which are optimized to provide the desired level of BACKGROUND OF THE INVENTION Solubility, Substantivity, and de-aggregation. These two ele It is known that certain water-Soluble phthalocyanine, 25 ments will be described in more detail herein below. naphthalocyanine, and metallocyanine compounds can be One key to this ability to control the molecular properties used as photobleaching and anti-microbial agents. Phthalo is found when contrasting the Structure of known pho cyanines and naphthalocyanines or their metal complexes tobleaches comprising phthalocyanines and naphthalocya can form “singlet oxygen an oxidative Species capable of nines with those of the present invention. The examples of reacting with Stains to bleach them to a colorleSS and usually photo-bleaches previously described in the art are generally water-Soluble State. flat molecules due to their planar ring structure. This pla There are many examples of phthalocyanines and naph narity produces an propensity for these molecules to aggre thalocyanines photobleaches, the most common being the tate wherein this aggregation tends to lead to photochemical Zinc and aluminum phthalocyanines. In the literature the quenching, preventing efficient formation of Singlet oxygen. term “photosensitizer” is often used instead of “photoacti 35 The organotin, organogermanium, organoplatinum, Vator” and may therefore be considered as Standing equally organopalladium, organolead, or organophosphorous photo well for the latter term used throughout this specification Sensitizing compounds of the present invention comprise The prior art teaches phthalocyanine and naphthalocya axial Substituents that act to break up this ordering effect, nine compounds having the general Structure hence providing an efficiently formed mono-layer of pho 40 toSensitizers evenly applied to a given Substrate. Because each molecule of this mono-layer can now contribute to Y bleaching there is better cost efficiency to the formulator. Me(Sens.) It has been Surprisingly found that because of the Sepa rating out of physical properties into "molecular Sectors', 45 e.g. R groups for Solubility, new uses for the compounds of the present invention have been realized. Adducts which where Me is a transition or non-transition metal, (Sens.) is provide unique solubility profiles, but which detract from a phthalocyanine or naphthalocyanine ring which, when the photophysics, were once excluded from use in pho combined with a Suitable Me unit, is capable of undergoing tobleaches. However, the inclusion of these moieties into the photoSensitization of oxygen molecules, R units are Sub 50 photobleaches of the present invention results in the ability Stituent groups which are bonded to the photosensitization to formulate photobleaches for use in non-classical ring units (Sens.) to enhance the Solubility or photochemical applications, for example dry cleaning applications. Solvent properties of the molecule, and Y units are Substituents based or low aqueous Solutions of the present invention are asSociated with the metal atom, for example, anions to now obtainable for the very reason that the present invention provide electronic neutrality. The Selection of a particular 55 provides control over solubility which is manifested in the Substituent R unit for Substitution into the molecule has been choice of the axial R Substitutions. the focus of many years of research and these units are The proper Selection of axial R units attached to the typically chosen by the formulator to impart into the target compounds of the present invention allow the formulator to molecule the desired level of water solubility. balance the changes in photoefficiency of the desired com A major limitation to the use of phthalocyanine and 60 pound with the water solubility of the parent material. In naphthalocyanine compounds for fabric photobleaching is addition, these axial R unit modifications provide the for the fact that these molecules are highly colored materials. mulator with the ability to balance Solubility, Q-band ), A Second limitation is that the compounds are not inher and quantum efficiency of the (Sens.) unit. ently water soluble. It has therefore been the task of phtha It is an object of the present invention to provide “sub locyanine and naphthalocyanine photobleach formulators to 65 Stantive' and "non-Sub Stantive' organo tin, provide water soluble photobleaches without adversely organogermanium, organoplatinum, organopalladium, affecting their photochemical properties. organolead, or organophosphorous photoSensitizers. A "Sub US 6,417,150 B2 3 4 Stantive' organotin, organogermanium, organoplatinum, J. Chem. Soc. Perkin Trans. I, Cook, M. J., et al., pg. 2453, organopalladium, organolead, or organophosphorous photo (1988); Acc. Chem. Res., Sayer, P., Gouterman, M., and Sensitizer will be attracted to a Surface and a “non Connell, C. R., 15, 73–79, (1982); J. Am. Chem. Soc., Snow, Substantive' organotin, organogermanium, organoplatinum, A. W. and Jarvis, N. Lynn, 106, 4706–4711, (1986); J. Am. organopalladium, organolead, or organophosphorous photo Chem. Soc., Richter, B. D., Kenney, M. E., Ford, W. E. and Sensitizer will repel a Surface. Rodgers, M. A. J., 112,8064-8070, (1990); Cancer Letters, It is a further object of the present invention to provide Soncin M., Polo, L., Reddi, E., Jori, G., Kenny, M. E., Substantive and non-Substantive photobleaching laundry Chang, G., and Rodgers, M. A. J., 89, 101-106, (1995); J. compositions for natural, Synthetic or blended fabrics. Inorg, Nucl. Chem., Rafaeloff, R., Kohl, F.J., Krueger, P. C., It is a further object of the present invention to provide Kenney, M. E., 28, 899–902, (1966); J. Amer: Chem. Soc., photobleaching compositions that comprise non-aqueous Dirk, C. W., Inabe, T., Schoch, Jr., K. F., and Marks, T. J., and low aqueous carriers, that is, photobleaching composi 105, 1539–1550, (1985); Polyhedron, Nyaokong, T., tions having carriers wherein water constitutes less than half 2067-71, (1994); Angew. Chem., Int. Ed. Engl., Kato, S., of the carrier liquid. Noda, I., Mizuta, M. M., and Itoh, Y., 18, 82-3, (1979); It is a further object of the present invention to provide 15 Photochemistry and Photobiology, Chan, W.-S., Marshall, J. Substantive and non-Substantive photobleaching hard Sur F., Svensen, R., Phillips, D., and Hart, I. R., 45, 757-61, face cleaning compositions for non-porous hard Surfaces, (1987); Inorganica Chemica Acta, Kraut, B., and Ferrandi, inter alia, FormicaE), ceramic tile, glass, or for porous hard G., 149, 273–77, (1988); Inorg. Chem., Kroenke, W.J., and Surfaces Such as concrete or wood. Kenney, M. E., 3, 251-4, (1964). An object of the present invention is to provide a method for bleaching fabric with laundry compositions comprising SUMMARY OF THE INVENTION organo tin, organoger manium, organoplatinum, The present invention relates to a photochemical Singlet organopalladium, organolead, or organophosphorous pho oxygen generator having a Q-band maximum absorption tobleaching compounds of the present invention. wavelength of 660 nanometers or greater, having the for An object of the present invention is to provide a method 25 mula: for cleaning hard Surfaces with compositions comprising organo tin, organoger manium, organoplatinum, organopalladium, organolead, or organophosphorous pho R2 tobleaching compounds of the present invention. 2. An object of the present invention is to provide for low R ly hue organotin, organogermanium, organoplatinum, organopalladium, organolead, or organophosphorous photo R --> Sensitizing compounds having a Q-band maximum absorp / N N \ tion wavelength of at least 660 nanometers. N Rif IIM-R N 35 / N BACKGROUND ART N N Various patent documents relate to photochemical bleach R4 R4 ing or to the use of phthalocyanine and naphthalocyanine eas-s-s-y compounds as well as their formulation and Synthesis. See R3-- HR: for example U.S. Pat. No. 3,094,536 issued Jun. 18, 1963; 40 U.S. Pat. No. 3,927,967 issued Dec. 23, 1975; U.S. Pat. No. RSax R RS-X. R 4,033,718 issued Jul. 5, 1977; U.S. Pat. No. 4,166,718 issued Sep. 4, 1979; U.S. Pat. No. 4,240,920 issued Dec. 23, or the formula: 1980; U.S. Pat. No. 4,255.273 issued Mar. 10, 1981; U.S. Pat. No. 4,256,597 issued Mar. 17, 1981; U.S. Pat. No. 45 R6 R5 4,318,883 issued Mar. 9, 1982: U.S. Pat. No. 4,368,053 "Ra R6 an issued Jan. 11, 1983; U.S. Pat. No. 4,497,741 issued Feb. 5, R4r S/S 1985; U.S. Pat. No. 4,648,992 issued Mar. 10, 1987; and U R1 R1 27.y U.K. Pat. App. 1,372,035 published Oct. 30, 1974; U.K Pat. Y-y N App. 1,408,144 published Oct. 1, 1975; U.K. Pat App. 50 X. 2,159,516 published Dec. 4, 1985; E.P. 484,027 A1 pub lished May 6, 1992; WO91/18006 published Nov. 28, 1991 R2 R2 and Japanese Kokai 06-73397 Derwent Abst. No. (94 128933) published Mar. 15, 1994. / N N \ N Riic II. Mrs.R In addition to the above cited patent publications, other 55 / N references describing the Synthesis, preparation and proper N N ties of phthalocyanines and naphthalocyanines, incorporated R2 N herein also by reference; Phthalocyanines. Properties and 2X1 N N Applications, Leznoff, C. C. and Lever A. B. P. (Eds), VCH, R4 1989, Infrared Absorbing Dyes, Matsuoka, M. (Ed), 60 S S/S % Plenum, 1990; Inorg. Chem., Lowery, M.J. et al., 4, pg. 128, f X. R1 (1965); Inorg. Chem. Joyner R. D. et al., 1, pg. 236, (1962); ya i. Inorg. Chem., Kroenke, W. E. et al., 3, 696, 1964, Inorg. SASx Chem. Esposito, J. N. et al., 5, pg. 1979, (1966); J. Am. &x. R6 Chem. Soc. Wheeler, B. L. et al., 106, pg. 7404, (1984); 65 Inorg. Chem. Ford, W. E., et al., 31, pg. 3371, (1992); wherein M is a photoactive metal or non-metal, Said metal Material Science, Witkiewicz, Z. et al., 11, pg. 39, (1978); or non-metal Selected from the group consisting of Sn, Ge, US 6,417,150 B2 S 6 Pt, Pd, Pb, P and mixtures thereof; R', R. R. R", R, and p) an alkyleneamino unit of the formula: R units are each independently selected from the group consisting of: R10 a) hydrogen; b) halogen; c) hydroxy, R11 d) C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; wherein R'' and R'' are C-C alkyl, C-C, e) halogen Substituted C-C alkyl, C-C branched 1O branched alkyl, C-C alkenyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or alkenyl, or mixtures thereof; R' is: mixtures thereof; i) hydrogen; f) polyhydroxyl Substituted C-C alkyl, ii) C-C alkyl, C-C branched alkyl, C-C2 g) C-C alkoxy; alkenyl, C-C branched alkenyl, or mixtures h) branched alkoxy having the formula: 15 thereof; A is nitrogen or oxygen; X is chlorine, bromine, iodine, CH-(O)(CH2)(OCH2CH2); Z. or other water Soluble anion, V is 0 or 1, u is from 0 to 22; -O-CH O q) an amino unit of the formula: CH-(O)(CH2)(OCH2CH2); Z. -NR17R18 -O-CH wherein R'' and R' are C-C alkyl, C-C, branched alkyl, C-C alkenyl, C-C branched CH-(O).(CH2)(OCH2CH3); Z. 25 alkenyl, or mixtures thereof; r) an alkylethyleneoxy unit of the formula: wherein Z is hydrogen, hydroxyl, C-Co alkyl, -(A)-(CH),(OCH-CH).Z. C-C alkoxy, -COH, -OCH-COH, -SOM, –OSOM', -POM, —OPOM, or mixtures wherein Z is: thereof; M is a water Soluble cation in Sufficient amount i) hydrogen; to Satisfy charge balance, X is 0 or 1, each y indepen ii) hydroxyl; dently has the value from 0 to 6, each Z independently iii) -COH; has the value from 0 to 100; iv) -SOM"; i) Substituted aryl, unsubstituted aryl, or mixtures thereof; 35 v) –OSOM t; j) Substituted alkylenearyl, unsubstituted alkylenearyl, or Vi) C-C alkoxy; mixtures thereof; vii) Substituted aryl, unsubstituted aryl, or mixtures k) Substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; thereof; viii) Substituted aryloxy, unsubstituted aryloxy, or mix 40 tures thereof; 1) Substituted oxyalkylene aryl, unsubstituted ix) alkyleneamino; or mixtures thereof; oxyalkylenearyl, or mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, V m) Substituted alkylene oxyaryl, unsubstituted is 0 or 1, X is from 0 to 100, y is from 0 to 12; alkyleneoxyaryl, or mixtures thereof; s) substituted siloxy of the formula: n) C-C thioalkyl, C-C branched thioalkyl, or mix 45 tures thereof; OSiR1R20R21 o) an ester of the formula -COR wherein R is i) C-C alkyl, C-C branched alkyl, C-C2 wherein each R', R', and R is independently alkenyl, C-C branched alkenyl or mixtures i) C-C alkyl, C-C branched alkyl, C-C, thereof; 50 alkenyl, C-C branched alkenyl, or mixtures ii) halogen Substituted C-C alkyl, C-C branched thereof; alkyl, C-C alkenyl, C-C branched alkenyl, or ii) Substituted aryl, unsubstituted aryl, or mixtures mixtures thereof; thereof; iii) polyhydroxyl Substituted C-C alkylene; iii) Substituted aryloxy, unsubstituted aryloxy, or mix iv) C-C22 glycol, 55 tures thereof; V) C-C alkoxy; iv) an alkylethyleneoxy unit of the formula: Vi) C-C branched alkoxy; Vii) Substituted aryl, unsubstituted aryl, or mixtures -(A)-(CH),(OCH-CH).Z. thereof; wherein Z is: viii) substituted alkyle neary 1, unsubstituted 60 a) hydrogen; alkylenearyl, or mixtures thereof; b) hydroxyl; ix) Substituted aryloxy, unsubstituted aryloxy, or mix c) -COH; tures thereof; d) -SOM"; X) Substituted oxyalkylene aryl, unsubstituted e) —OSOM t; oxyalkylenearyl, or mixtures thereof; 65 f) C-C alkoxy; Xi) Substituted alkylene oxyaryl, unsubstituted g) Substituted aryl, unsubstituted aryl, or mixtures alkyleneoxyaryl, or mixtures thereof; thereof; US 6,417,150 B2 7 8 h) Substituted aryloxy, unsubstituted aryloxy, or mix iii) polyhydroxyl Substituted C-C alkylene; tures thereof; iv) C-C glycol, i) alkyleneamino; or mixtures thereof; V) C-C alkoxy; A is nitrogen or oxygen, M is a water Soluble cation, Vi) C-C branched alkoxy; v is 0 or 1, X is from 0 to 100, y is from 0 to 12; vii) Substituted aryl, unsubstituted aryl, or mixtures and mixtures thereof axial R units wherein each R is thereof; independently Selected from the group consisting of viii) substituted alkyle neary 1, unsubstituted alkylenearyl, or mixtures thereof; a) hydrogen; ix) Substituted aryloxy, unsubstituted aryloxy, or mix b) halogen; 1O tures thereof; c) hydroxy, X) Substituted oxyalkylene aryl, unsubstituted d) C-C alkyl, C-C branched alkyl, C-C alkenyl, oxyalkylenearyl, or mixtures thereof; Xi) Substituted alkylene oxyaryl, unsubstituted C-C branched alkenyl, or mixtures thereof; alkyleneoxyaryl, or mixtures thereof; e) halogen Substituted C-C alkyl, C-C branched 15 alkyl, C-C alkenyl, C-C branched alkenyl, or p) an alkyleneamino unit of the formula: mixtures thereof; f) polyhydroxyl Substituted C-C alkyl, R10 g) C-C2 alkoxy; - (A) -(CH2) h) branched alkoxy having the formula: R11

CH-(O)(CH2)(OCH2CH2); Z. wherein R'' and R'' are C-C alkyl, C-C, -O-CH O 25 branched alkyl, C-C alkenyl, C-C branched CH-(O).(CH2)(OCH2CH3); Z. alkenyl, or mixtures thereof; R is: -O-CH i) hydrogen; CH-(O)(CH2)(OCH2CH3); Z. ii) C-C alkyl, C-C branched alkyl, C-C2 alkenyl, C-C branched alkenyl, or mixtures CH-(O)(CH2)(OCH2CH2); Z. thereof; A is nitrogen or oxygen; X is chlorine, bromine, iodine, wherein Z is hydrogen, hydroxyl, C-C alkyl, or other water Soluble anion, V is 0 or 1, u is from 0 to C-C alkoxy, -COH, -OCH-COH, -SOM, 35 22; –OSOM', -POM, —OPOM, or mixtures q) an amino unit of the formula: thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y indepen -NR17R18 dently has the value from 0 to 6, each Z independently has the value from 0 to 100; 40 wherein R'' and R' are C-C alkyl, C-C, i) Substituted aryl, unsubstituted aryl, or mixtures thereof; branched alkyl, C-C alkenyl, C-C branched j) Substituted alkylenearyl, unsubstituted alkylenearyl, or alkenyl, or mixtures thereof; mixtures thereof; r) an alkylethyleneoxy unit of the formula: k) Substituted aryloxy, unsubstituted aryloxy, or mixtures 45 thereof; -(A)-(CH2)(CHCH),Z j) Substituted oxyalkylene aryl, unsubstituted oxyalkylenearyl, or mixtures thereof; wherein Z is: m) Substituted alkylene oxyaryl, unsubstituted i) hydrogen; alkyleneoxyaryl, or mixtures thereof; 50 ii) hydroxyl; iii) -COH: n) C-C thioalkyl, C-C branched thioalkyl, or mix iv) -SOM"; tures thereof; v) –OSOM t; o) a carboxylate of the formula: Vi) C-C alkoxy; 55 vii) Substituted aryl, unsubstituted aryl, or mixtures O thereof; viii) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; ix) alkyleneamino; or mixtures thereof; wherein R is: 60 A is nitrogen or oxygen, M is a water Soluble cation, V i) C-C alkyl, C-C branched alkyl, C-C, is 0 or 1, X is from 0 to 100, y is from 0 to 12; alkenyl, C-C branched alkenyl, or mixtures s) substituted siloxy of the formula: thereof; OSiR19R20R21 ii) halogen Substituted C-C alkyl, C-C branched 65 alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; wherein each R', R', and R is independently US 6,417,150 B2 9 10 i) C-C alkyl, C-C branched alkyl, C-C2 or naphthalocycanines having the formula: alkenyl, C-C branched alkenyl, or mixtures thereof; ii) Substituted aryl, unsubstituted aryl, or mixtures ey thereof; iii) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; y 2% iv) an alkylethyleneoxy unit of the formula: ex, -(A)-(CH),(OCH-CH).Z.

wherein Z is: ^ N a) hydrogen; 15 2 b) hydroxyl; c) -COH; d) -SOM; R3-- e) —OSOM t; U Sa ? S. S1 4. f) C-C alkoxy; na a 6 y x g) Substituted aryl, unsubstituted aryl, or mixtures thereof; h) Substituted aryloxy, unsubstituted aryloxy, or mix wherein M is a photoactive metal or non-metal, Said metal tures thereof; 25 or non-metal Selected from the group consisting of Sn, Ge, i) alkyleneamino, or mixtures thereof; Pt, Pd, Pb, P, and mixtures thereof. The phthalocyanine and A is nitrogen or oxygen, M is a water Soluble cation, naphthalocyanine rings which comprise the photo Sensitiz v is 0 or 1, X is from 0 to 100, y is from 0 to 12; ers of the present invention, can be substituted with hydro gen or other units described further herein below. and mixtures thereof. Surprisingly, selection of a suitable R', R,R,R,R, or R All percentages, ratioS and proportions herein are by Substituent is capable of providing the photobleach or pho weight, unless otherwise Specified. All temperatures are in todisinfectant with a positive A, yield of at least 1, degrees Celsius ( C.) unless otherwise specified. All docu preferably at least 10, more preferably at least 30, when said ments cited are, in relevant part, incorporated herein by 35 moiety replaces a hydrogen atom. In addition, the Selection reference. of a suitable moiety for a R', R. R. R", R, or R Substituent is also capable of providing a positive red shift value of at least 1, preferably a positive red shift value of at least 10, more preferrably a positive red shift value of at least DETAILED DESCRIPTION OF THE 40 30, when said moieties are substituted for hydrogen. INVENTION Each R', R, R, R, R, and R unit is independently: a) hydrogen; The present invention relates to photobleaching com b) halogen; pounds and photobleaching compositions. The photobleach 45 c) hydroxyl, ing compounds have a Q-band maximum absorption wave d) C-C alkyl, C-C branched alkyl, C-C alkenyl, length of 660 nanometers or greater. The photobleaching and C-C branched alkenyl, photodisinfectants of the present invention are phthalocya e) halogen Substituted C-C alkyl, C-C branched nies having the formula: 50 alkyl, C-C alkenyl, C-C branched alkenyl, f) polyhydroxyl Substituted C-C alkyl, g) C-C alkoxy, preferably C-C alkoxy, more pre ferred methoxy; 55 h) branched alkoxy having the formula

N Rii MassR N 60 CH-(O)(CH2)(OCH2CH2); Z. R3 2.e s N i -O-CH -x. -x. 65 US 6,417,150 B2 11 wherein Z is hydrogen, hydroxyl, C-Co linear alkyl, C-C branched alkyl, C-Co alkoxy, -CO2H, –OCH-COH, -SOM', -OSOM', -POM, -O(CH2). / y -OPOM, and mixtures thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y independently has the value from 0 to 6, preferably from 0 to 6; each Z indepen wherein R' and R'' are as defined above, w is from dently has the value from 0 to 100, preferably from 0 about 1 to about 10. to about 10, more preferably from 0 to about 3; n) C-C linear, C-C branched thioalkyl, C-C, linear, C-C branched Substituted thioalkyl, and mix i) Substituted aryl, and unsubstituted aryl having the tures thereof; formula: o) ester units of the formula -COR wherein R is C-C alkyl, C-C branched alkyl, C-C alkenyl, 13 15 C-C branched alkenyl, all of which can be Substi / ;" tuted with halogen; poly-hydroxyl Substituted C-C, o R14 alkyl, C-C22 glycol, C-C22 alkoxy, C-C22 branched alkoxy; Substituted and unsubstituted aryl, alkylene aryl, aryloxy, oxyalkylene aryl, alkyle wherein R' and R'' are independently selected from neoxyaryl; preferably C-C alkyl, C-C branched the group consisting of hydrogen, C-C alkyl, C-C, alkyl, and mixtures thereof; alkenyl, C-C alkoxy, C-C branched alkoxy, p) alkyleneamino units having the formula: halogen, -COM", -SOM', -OSOM", R10 -N(R'), and -N"(R').X wherein each R" is 25 independently hydrogen or C-C alkyl, and mixtures - (A) (CH) N-R12 X thereof; preferably hydrogen C-C alkyl, -COM", -SOM', -OSOM", and mixtures thereof, more R11 preferably R' or R' is hydrogen and the other moiety is C-C alkyl, wherein M is a water Soluble cation and wherein R', and R'' are each a C-C-2 alkyl, C-C2 X is a water Soluble anion. branched alkyl, C-C alkenyl, C-C branched alkenyl, R' is hydrogen, C-C alkyl, C-C2 j) Substituted alkylenearyl and unsubstituted alkylenearyl branched alkyl, C-C alkenyl, C-C branched alk having the formula: enyl and mixtures thereof, the index v is 0 or 1; X is a 35 other water soluble anion, u is from 0 to 22, preferably S- R13 u is from 3 to about 10. Examples of water soluble o (CH2)5 / Q anions include organic Species Such as fumarate, o R14 tartrate, oxalate and the like, inorganic Species include chloride, bromide, Sulfate, hydrogen Sulfate, phosphate 40 and the like; wherein R' and R'' are as defined above, p is from 1 q) an amino unit of the formula to about 10. -NR17R18 k) Substituted aryloxy and unsubstituted aryloxy having the formula: 45 wherein R'' and R' are each a C-C alkyl, C-C, branched alkyl C-C alkenyl, C-C branched R13 alkenyl, or mixtures thereof; r) alkylethyleneoxy units having the formula: -o-( - SSR" 50 -(A)-(CH2)(OCH2CH2), Z. wherein R' and R'' are as defined above. wherein Z is hydrogen, hydroxyl, -COH, -SOM, 1) Substituted alkyleneoxyaryl and unsubstituted alkyle -OSOM, C-C alkoxy, Substituted and unsubsti neoxyaryl units are defined as moieties having the 55 tuted aryl, Substituted and unsubstituted aryloxy; alky formula: leneamino as defined herein above; or mixtures thereof; A units comprise nitrogen or oxygen, preferably oxy gen; M is a water Soluble cation; V is 0 or 1, X is from 0 to 100, preferably from 0 to 20, more preferably from 60 0 to 5; y is from 0 to 12, preferably from 1 to 4; however, no peroxide -O-O-bonds are contained within the photobleaching compounds of the present wherein R' and R'' are as defined above, q is from 0 invention; to about 10. s) siloxy and substituted siloxy of the formula 65 - OSiR'R'R' wherein each R', R', and R’ is m) Substituted oxyalkylenearyl and unsubstituted oxy independently Selected from the group consisting of alkylenearyl having the formula: C-C alkyl, C-C branched alkyl, C-C alkenyl, US 6,417,150 B2 13 14 C-C branched alkenyl, or mixtures thereof, Substi alkenyl, C-C alkoxy, C-C branched alkoxy, tuted or unsubstituted aryl, aryloxy; alkylethyleneoxy halogen, -COM", -SOM', -OSOM", units of the formula: -N(R'), and -N"(R').X wherein each R" is independently hydrogen or C-C alkyl, and mixtures -(A)-(CH2)(OCH2CH2), Z. thereof; preferably hydrogen C-C alkyl, -COM", -SOM', -OSOM", and mixtures thereof, more wherein Z is hydrogen, hydroxyl, C-Co alkyl, preferably R' or R' is hydrogen and the other moiety -COH, -SOM', -OSOM", C-C alkoxy; is C-C alkyl, wherein M is a water Soluble cation and Substituted or unsubstituted aryl, and aryloxy; alkyle X is a water Soluble anion. neamino as defined herein above, and mixtures thereof, j) Substituted alkylenearyl and unsubstituted alkylenearyl preferably hydrogen or C-C alkyl, more preferably having the formula: methyl; V is 0 or 1; x is from 1 to 100, preferably from 0 to about 20, more preferably from 3 to about 10; and y is from 0 to 12, preferably from about 0 to about 5. / x 13 Preferred R', R. R. R', R, and R units are C-C, 15 - (CH) alkoxy and halogen, more preferred R', R. R. R', R, and \ S. R units are C-C alkoxy and halogen. When the (Sens.) unit is phthalocyanine most preferred R', R, R, and R' units are methoxy. When the (Sens.) unit is naphthalocya wherein R' and R'' are as defined above, p is from 1 nine most preferred R', R, R, R, R, and R units are to about 10. chlorine, bromine or iodine. k) Substituted aryloxy and unsubstituted aryloxy having The compounds useful for the present invention also the formula: comprise axial R units, wherein R is independently Selected from the group consisting of: R13 a) hydrogen; 25 b) halogen; -o-( - SSR" c) hydroxyl, d) C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, wherein R' and R'' are as defined above. e) halogen Substituted C-C alkyl, C-C branched 1) Substituted alkyleneoxyaryl and unsubstituted alkyle alkyl, C-C alkenyl, C-C branched alkenyl, neoxyaryl units are defined as moieties having the f) polyhydroxyl Substituted C-C alkyl; formula: g) C1-C alkoxy, preferably C-C alkoxy, more pre ferred methoxy; 35 W R13 h) branched alkoxy having the formula o (CH2)O / X S R14

-O-CH O 40 wherein R' and R'' are as defined above, q is from 0 to about 10. CH-(O)(CH2)(OCH2CH2); Z. m) Substituted oxyalkylenearyl and unsubstituted oxy -O-CH alkylenearyl having the formula: 45 VR

o R14 wherein Z is hydrogen, hydroxyl, C-Co linear alkyl, C-C branched alkyl, C-C alkoxy, -COH, 50 –OCH-COH, -SOM', -OSOM', -POM, wherein R' and R'' are as defined above, w is from -OPOM, and mixtures thereof; M is a water about 1 to about 10. Soluble cation in Sufficient amount to Satisfy charge n) C-C linear, C-C branched thioalkyl, C-C2 balance, X is 0 or 1, each y independently has the value linear, C-C branched Substituted thioalkyl, and mix from 0 to 6, preferably from 0 to 6; each Z indepen 55 tures thereof; dently has the value from 0 to 100, preferably from 0 o) carboxylate units of the formula to about 10, more preferably from 0 to about 3; i) Substituted aryl, and unsubstituted aryl having the O formula: 60 R13 wherein R is C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, all of which = 7 R can be Substituted with halogen; poly-hydroxyl Substi 65 tuted C-C22 alkyl, C-C22 glycol, C-C22 alkoxy, wherein R' and R'' are independently selected from C-C branched alkoxy; Substituted and unsubstituted the group consisting of hydrogen, C-C alkyl, C-C, aryl, alkylenearyl, aryloxy, oxyalkylenearyl, alkyle US 6,417,150 B2 15 16 neoxyaryl; preferably C-C alkyl, C-C branched Y is a linking moiety Selected from the group consisting alkyl, and mixtures thereof; of O, CRR, OSiRR, OSnRR, and mixtures p) alkyleneamino units having the formula: thereof; wherein R and R are hydrogen, C-C, alkyl, halogen, and mixtures thereof; i is 0 or 1, j is R10 5 from 1 to 3; K is a ligand Selected from the group consisting of: a) C-C linear alkyl, C-C branched alkyl, C-Co linear alkenyl, C-C branched alkenyl, Co-Co R11 aryl, C7-Co arylalkyl, C7-Co alkylaryl, and mix 1O tures thereof; wherein R', and R' are each a C-C alkyl, C-C, b) an alkylethyleneoxy unit of the formula branched alkyl, C-C alkenyl, C-C branched alkenyl, R' is hydrogen, C-C alkyl, C-C, branched alkyl, C-C alkenyl, C-C branched alk wherein Z is Selected from the group consisting of enyl and mixtures thereof, the index v is 0 or 1; X is a 15 hydrogen, C-C alkyl, C-C branched alkyl, other water soluble anion, u is from 0 to 22, preferably C-C linear alkenyl, C-C branched alkenyl, u is from 3 to about 10. Examples of water soluble Co-Co aryl, C7-Cao arylalkyl, Co-Co alkylaryl, anions include organic Species Such as fumarate, and mixtures thereof; R’ is selected from the group tartrate, oxalate and the like, inorganic Species include consisting of C-C linear alkylene, C-C branched chloride, bromide, Sulfate, hydrogen Sulfate, phosphate alkylene, C-C hydroxyalkylene, and mixtures and the like; thereof; R is selected from the group consisting of q) an amino unit of the formula C-Co alkylene, Cs-Cobranched alkylene, Co-Co arylene, C7-Co arylalkylene, C7-Co alkylarylene, and mixtures thereof; x is from 1 to 100; y is 0 or 1; 25 and wherein R7 and Rare each a C-C alkyl, C-C, Q is an ionic moiety having the formula: branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; -R W alkylethyleneoxy units having the formula: wherein R is selected from the group consisting of -(A)-(CH2)(OCH2CH2), Z. C-Co linear alkylene, C-C branched alkylene, C-C linear alkenylene, C-C branched wherein Zis hydrogen, hydroxyl, -COH, -SOM", alkenylene, C-C arylene, and mixtures thereof; W is -OSOM, C-C alkoxy, Substituted and unsubsti selected from the group consisting of -COM", tuted aryl, Substituted and unsubstituted aryloxy; alky 35 –SOM', -OSOM"; POM', -OPOM", leneamino as defined herein above; or mixtures thereof; -N"(R°7)X; wherein R°7 is independently A units comprise nitrogen or oxygen, preferably oxy hydrogen, C-C alkyl, -(CH), OH, -(CHCHO), gen; M is a water Soluble cation; V is 0 or 1, X is from H, and mixtures thereof, wherein n is from 1 to 4, M is 0 to 100, preferably from 0 to 20, more preferably from a water Soluble cation of Sufficient charge to provide 0 to 5; y is from 0 to 12, preferably from 1 to 4; 40 electronic neutrality and X is a water Soluble anion as however, no peroxide -O-O-bonds are contained defined herein above. within the photobleaching compounds of the present Preferred axial R units are alkyl alkyleneoxy units of the invention; formula s) siloxy and substituted siloxy of the formula 45 - OSiR'R'R'' wherein each R', R', and R is independently Selected from the group consisting of wherein Z is Selected from the group consisting of hydrogen, C-C alkyl, C-C branched alkyl, C-C alkenyl, C7-Co linear alkyl, C-C branched alkyl, C-C linear C-C branched alkenyl, or mixtures thereof, Substi alkenyl, C-C branched alkenyl, C-C aryl, C7-Co tuted or unsubstituted aryl, aryloxy; alkylethyleneoxy 50 arylalkyl, C7-Co alkylaryl, and mixtures thereof; Rif is units of the formula: Selected from the group consisting of C-C linear alkylene, C-C branched alkylene, and mixtures thereof; R is -(A)-(CH2)(OCH2CH2), Z. Selected from the group consisting of C-C alkylene, C-C branched alkylene, Co-Co arylene, and mixtures wherein Z is hydrogen, hydroxyl, C-Co alkyl, 55 thereof; x is from 1 to 50; y is 0 or 1. -COH, -SOM', -OSOM", C-C alkoxy; More preferred axial R units comprise y equal to 0, Z is Substituted or unsubstituted aryl, and aryloxy; alkyle hydrogen, C-Co alkyl, C-C branched alkyl, Co-Co neamino as defined herein above, and mixtures thereof, aryl, and mixtures thereof, most preferred Z is hydrogen or preferably hydrogen or C-C alkyl, more preferably Co-Co linear alkyl, Co-Co branched alkyl; Rf is C-C, methyl; V is 0 or 1; x is from 1 to 100, preferably from 60 linear or C-C branched alkylene. 0 to about 20, more preferably from 3 to about 10; and Also preferred R units having the formula: y is from 0 to 12, preferably from about 0 to about 5. According to the present invention the preferred axial R units comprise moieties having the formula wherein Y is a linking moiety Selected from the group 65 consisting of O, CRR OSiRR, OSnRR, and -Y-K, and -Y-Qi mixtures thereof; i is 0 or 1, j is from 1 to 3; Q is an ionic wherein moiety having the formula: US 6,417,150 B2 17 wherein R is selected from the group consisting of C-Co linear alkylene, C-C branched alkylene, C-Co linear alkenylene, C-C branched alkenylene, C-C arylene, and mixtures thereof; W is Selected from the group consist ing of -COM', -SOM', -OSOM"; POM", –OPOM', -N (R-7).X; wherein R-7 is independently hydrogen, C-C alkyl, -(CH),OH, -(CH2CH2O).H., and mixtures thereof, wherein 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 herein above. A preferred hydrophilic R has the index i equal to 1; R' is C-Co linear alkylene, C-C branched alkylene; W is 15 -COM', -SOM', -OSOM"; M is a water soluble cation of Sufficient charge to provide electronic neutrality. Examples of Yunits suitable for use in R units having the formula:

-Y-K, have the formula 25 which contain the same R' and Runit substitutions, are also -O-K", -S-K", -OSn-K' equivalent for the purposes of the present invention and the Selection of either one structure over the other will not effect wherein i is equal to 1 and j is equal to 1. Further examples the desired properties of the molecule described herein. The have the formula above examples, however, are only representative of the total number of equivalent Structure examples that will be Kl Kl recognized by those skilled in the art. Compounds useful for the present invention having Sub l-k -o-k stituted one or more R', R, R, and R', unit, as in the case k k of phthalocyanine, or R', R. R. R", R, and Runit, as in 35 the case of naphthalocyanines, which have their Substitu tions oriented in a manner described by the following wherein i is equal to 1 and j is equal to 3. The above formula

examples also apply to Y units when used with Q ionic moieties. When compounds of the present invention have present 40 one or more substituent R', R, R, and R', units, as in the case of phthalocyanine, or R', R. R. R", R, and Runits, 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, certain 45 equivalencies of Substitution exist. For example, the two units of the following formula

50 are not equivalent for the purposes of the present invention and would each constitute Separate compounds regardless of the fact that the R' and R units are equivalent. The above example does not exhaust the number of non-equivalent 55 structures that are possible using any combination of R', R, R. R", R, and R units recognized by those skilled in the art. Solublizing axial R units, are bonded directly to the central tin, germanium, platinum or palladium atom. Each R 60 unit can be chosen independently of the other. The Selection of an R unit is made, for example, to provide Solubility, which contain the same R' Substitution, are equivalent for non-solubility, “substantivity”, “non-substantivity” to the the purposes of the present invention and the Selection of compound. These are a few examples of the utility of the either one structure over the other will not effect the desired axial group and those skilled in the art will recognize that properties of the molecule described herein. 65 other properties of the photobleaches can be controlled via In addition, compounds containing the Substitution rep axial Substitution. R units are nonionic, cationic, or anionic resented by the following formulas units. US 6,417,150 B2 19 20 Below is an example of a preferred “substantive” embodi ment (has an affinity for Surfaces, e.g. fabric) of the present invention comprising a phthalocyanine ring System wherein at least one of the R', R, R, and R' units of each aromatic moiety is methoxy, each R group comprises an ethyleneoxy unit of the formula

1O wherein for each R unit Z is methoxy and X is 7.2 thereby giving the moiety an average ethoxylation value of 7.2. OSi(CH3)2(CH2)6SONa C OCH 15 N 2 OCH HCO(CHCHO).3CO(CH2CH2O)7 "juin, N -N \ N M N / N. SN N NOCHCH)OCH, Below is an example of a “non-substantive” embodiment CHO (charged R units reduces the affinity for Surfaces, e.g. fabric) N-N of the present invention comprising a naphthalocyanine ring system wherein at least one of the R', R. R. R', R, and CHO 25 R units of each aromatic moiety is bromine, and the R groups comprise an siloxy unit the formula -OSiRRR wherein R7 and R units are methyl and R is of the formula Below is an example of a “substantive” embodiment (has an affinity for Surfaces, e.g. fabric) of the present invention -(CH2)Z comprising a phthalocyanine ring System wherein at least wherein Z is -SOM', M is sodium and y is equal to six. two of the R', R, R, and R' units of each aromatic moiety is methoxy, each R group comprises an ethyleneoxy unit of Br Br the formula s N 2A 35

N a wherein for each R unit Z is methoxy and X is 7.2 thereby giving the moiety an average ethoxylation value of 7.2. NaO3S(CH2)6(CH3)2SiON N 40 7".N./ N V. OCHCHO NSa losiCH-CH, SON N N CHO 2 OCH HCO(CHCHO).3CO(CH2CH2O)7 "juin, N N 45 N M N A4 SN / NSociation, A B Br CHO s N OCH 50 The compounds of the present invention can be modified to have a wide range of Surface affinities. Molecules can be OCH, CHO made “substantive” or “non-substantive” by the choice of axial R units. The term “substantivity” as defined herein is the property which allows the photobleaching agent to Below is an example of a “non-substantive” embodiment 55 Successfully deposit on a targeted Surface. For example, the (charged R units reduces the affinity for Surfaces, e.g. fabric) axial groupSR, hereinafter defined in the Specification, may of the present invention comprising a naphthalocyanine ring be selected to provide compatibility of the photobleaching system wherein at least two of the R", R. R. R", R, and compound with a Synthetic fabric, a durable Surface Such as R units of each aromatic moiety are chlorine, one R group ceramic tile, or in general any fabric, article of manufacture 60 or Situs that is to be a target of photobleaching. comprises an siloxy unit the formula-OSiRRR wherein The present invention also relates to laundry detergent or R" and R units are methyl and R is of the formula hard Surface cleaning compositions comprising: A) at least about 0.1%, preferably from about 0.1% to about 30%, more preferably from about 1% to about 65 30%, most preferably from about 5% to about 20% by wherein Z is -SOM', M is sodium and y is equal to six; weight, of a detersive Surfactant, Said detersive Surfac the Second axial R unit is methoxy. tant is Selected from the group consisting of anionic, US 6,417,150 B2 21 22 cationic, nonionic, Zwitterionic, ampholytic remain in the liquor rather than becoming attracted to Surfactants, and mixtures thereof; a particular Surface, i.e. water Sterilization. B) at least about 0.001 ppm, preferably from about 0.01 The term “low hue' as used herein and throughout the to about 10000 ppm, more preferably from about 0.1 to Specification refers to photobleaches that have a 2 of their about 5000 ppm, most preferably form about 10 to Q-band above about 700 nm and are therefore only slightly about 1000 ppm, of a photosensitizing compound hav perceptible to the human eye. Those additional materials of ing a Q-band maximum absorption wavelength of 660 the present invention having Q-band maximum wavelengths nanometers or greater according to the present inven in the “visible” range, (i.e. 660-700 nanometers) are mate tion; and rials that are most Suitable when the perception of a colored C) the balance carriers and adjunct materials. material is not a factor in deterring utility. The present invention further relates to laundry detergent Effective photobleaching is predicated on the production or hard Surface cleaning compositions comprising: of a molecule of Singlet oxygen, a theory which has been A) at least about 0.1%, preferably from about 0.1% to extensively studied and is well understood by those skilled about 30%, more preferably from about 1% to about in the art of photobleaching. Because the Singlet oxygen 30%, most preferably from about 5% to about 20% by 15 Species is short-lived, having the photoSensitizing molecule weight, of a detersive Surfactant, Said detersive Surfac tant is Selected from the group consisting of anionic, in proximity to the stain or the microbe to be “attacked” is cationic, nonionic, Zwitterionic, ampholytic of primary advantage. Surfactants, and mixtures thereof; The molecules of the present invention because of the B) at least about 0.001 ppm, preferably from about 0.01 ability of the formulator to control “substantivity”, can be to about 10000 ppm, more preferably from about 0.1 to directed to any desired surface. The additional ability to about 5000 ppm, most preferably form about 10 to prevent layering and Stacking of photosensitizing molecules about 1000 ppm, of a photosensitizing compound hav due to the axial nature of the R units, provides for an efficient ing a Q-band maximum absorption wavelength of 660 mono-layer. For example, an embodiment of the present nanometers or greater according to the present inven invention for removing stains from a fabric will have the 25 requirements that the organotin, organogermanium, tion; wherein selection of a suitable moiety for a R', R, organoplatinum, organopalladium, organolead, or organo R. R", R, or R substituent is capable of providing the phosphorous photosensitizing compound have an affinity for photobleach or photodisinfectant with a positive Atrip the fabric Surface, and that the photobleaching compound be let yield of at least 1, preferably at least 10, more close to the desired site of action. These requirements are preferably at least 30, when Said moiety replaces a achieved by manipulation of one or more R units. hydrogen atom; and The present invention also relates to a process for carrying C) the balance carriers and adjunct materials. out a photo-Sensitized reaction or a reaction catalyzed by The present invention yet further relates to laundry deter Singlet oxygen, wherein one or more phthalocyanine or gent and hard Surface cleaning compositions comprising: naphthylocyanine compounds in the presence of oxygen, are A) at least about 0.1%, preferably from about 0.1% to 35 brought into contact with the medium in which or on which about 30%, more preferably from about 1% to about the Said reaction is to take place, or are incorporated in this 30%, most preferably from about 5% to about 20% by medium, and are irradiated with light. weight, of a detersive Surfactant, Said detersive Surfac It has long been known that phthalocyanine and naphtha tant is Selected from the group consisting of anionic, locyanine rings, can absorb light quanta and form electroni cationic, nonionic, Zwitterionic, ampholytic 40 cally excited Species (singlet and triplet) and that these Surfactants, and mixtures thereof; Species can be quenched by oxygen to yield excited oxygen B) at least about 0.001 ppm, preferably from about 0.01 Species. A particularly preferred excited oxygen Species is to about 10000 ppm, more preferably from about 0.1 to Singlet oxygen which is most reliably formed by the quench about 5000 ppm, most preferably form about 10 to ing of the triplet State of a photosensitizer, Such as a about 1000 ppm, of a photosensitizing compound hav 45 phthalocyanine, by molecular oxygen. It is therefore an aim ing a Q-band maximum absorption wavelength of 660 of the photobleach formulator to produce compounds that nanometers or greater according to the present inven favor the formation of the triplet state. tion; wherein selection of a suitable moiety for a R', R, When a photoSensitizer is irradiated with light, the Singlet R. R", R, or R substituent is capable of providing a energy State that results undergoes a variety of processes i.e. positive red shift value of at least 1, preferably a 50 re-emission of light (fluorescence). The most important positive red shift value of at least 10, more preferrably process with regard to photobleaching via Singlet oxygen is a positive red shift value of at least 30, when said inter system crossing (ISC). This is the mechanism by which moieties are Substituted for hydrogen; and the Singlet State is converted to the triplet State. In general, C) the balance carriers and adjunct materials the efficiency of this process is discussed in terms of Selection of a specific R moiety is generally made for 55 quantum yield, i.e. the number of photons absorbed that lead adjustment of the solubility or substantivity of the molecule. to the desired triplet eXcited State. The present invention For example, the R unit is matched to the Structural prop provides for increased photobleaching by modifying the erties of either the targeted material (i.e. fabric) or to the efficiency of inter System crossing from the Singlet State to targeted Substrate (i.e. stain). The option to tailor the prop the triplet State. The molecules of the present invention, can erties of the R unit to the material, is due to the ability to 60 be modified by the formulator to increase the quantum Select R units independently of effecting the phthalocyanine efficiency of triplet formation via the “heavy atom effect”. or naphthalocyanine ring. The selection of a moiety for its “heavy atom effect” can be An additional benefit of the photobleaching system of the made independently of other factors, for example, without present invention is that they are generally more fabric and undue concern for solubility factors. This is because the color safe than conventional bleaches (i.e. hypochlorite). 65 choice of axial R groups for Solubility will have no bearing “Non-substantive' molecules are desirable for applica on the changes made to the phthalocyanine or naphthalo tions where the photosensitizing compound must cyanine ring System. US 6,417,150 B2 23 24 The determination of the value of the Q-band wavelength ganic Substrates. It is further an object of the present and whether a shift occurs in this wavelength when a invention to protect the latter against attack by particular moiety (R', R. R. R", R or R unit) replaces a microorganisms, wherein the Substrates are treated with hydrogen atom on the phthalocyanine or naphthalocyanine phthalocyanines or naphthalocyanines of the present ring is Straight-forward. Typically, a Solution having a con invention, in the presence of water and while being irradi centration of approximately 1x10M of the phthalocyanine ated by light. or naphthalocyanine to be measured is prepared using a Another advantage of the present invention is the fact that Suitable Solvent (e.g. dimethylformamide) which contains 1 each R unit may be directed toward a separate desired wt % triton X-100. A UV/visible spectrum is then obtained property and the molecules of the present invention can and the Q-band) is recorded. This value is the "Substrate therefore be thought of as being “sided”. For example, one 2, A Spectrum for the material prior to introduction of axial R unit may be direct toward increased solubility while the Substituent group is obtained in the same manner. This the other axial R group may be chosen for its ability to value is the “reference 2'. The two spectra are com provide increase Substantivity. pared and the resulting measured values are placed into the The present invention also relates to a process for carrying following equation 15 out a photo-Sensitized reaction or a reaction catalyzed by Singlet oxygen, wherein one or more phthalocyanine or Wavelength red shift=AW =wn-wn. naphthylocyanine compounds in the presence of oxygen, are wherein if the number obtained is greater than or equal to 1, brought into contact with the medium in which or on which then the Substituent group has produced a positive red shift the Said reaction is to take place, or are incorporated in this of at least one nanometer and the Substituent is a preferred medium, and are irradiated with light. embodiments of the present invention. If the material of If the method is carried out in an aqueous medium (for interest is not soluble in dimethylformamide another suitable example the sterilization of textiles), the irradiation with Solvent may be used. light can either be carried out directly in the treatment Quantum yields and excited State energies are well known medium by means of an artificial Source of light mounted to those skilled in the art and the procedures for the 25 inside or outside the medium or the Substrates, in a moist determination of triplet quantum yield and like photophysi State, can Subsequently either be irradiated, again by means cal parameters are thoroughly described in the following of an artificial Source of light, or can be exposed to Sunlight. references Bonnet, R.; McGarvey, D.J.; Harriman, A.; Land, Good antimicrobial effects of the present compounds can be E. J.; Truscott, T. G.; Winfield, U-J. Photochem. Photobiol. achieved even with very low concentrations of active 1988, 48 (3), pg. 271-6; Davila, J., Harriman, A., Gulliya, K. Substance, for example at 0.001 ppm. Depending on the field S., Photochem. Photobiol., 1991, 53 (1), pg. 1-11; Davila, of use and on the phthalocyanine or naphthylocyanine J., Harriman, A., Photochem. Photobiol., 1989, 50 (1), pg. derivative employed, a concentration between 0.005 and 29-35; Charlesworth, P., Truscottt, T. G., Brooks, R. C., 100, preferably 0.01 and 50 ppm is preferable. The irradia Wilson, B.C., J. Photochem, Photobiol., part B 1994, 26 (3), tion can be effected by means of an artificial Source of light pg. 277-82; Zhang, X., Xu, H., J. Chem. Soc., Faraday 35 or by means of Sunlight. The intensity of the illumination can Trans., 1993, 89 (18), pg. 3347–51; Simpson, M. S. C., vary within wide limits, and it depends both on the concen Beeby, A., Bishop, S. M., MacRobert, A. J., Parker, A. W., tration of active as well as the nature of the light Source as Phillips, D., Proc. SPIE-int.Soc. Opt. Eng., 1992, 1640, pg. to the photobleaching efficiency of any particular compound 520–9; Phillips, D., Pure Appl. Chem., 1995, 67 (1), pg. of the present invention. A further parameter which can be 117–26; Wilkinson, F., Helman, W. P., Ross, A. B., J. Phys. 40 varied is the exposure time, i.e. for the same effect exposure Chem. Ref. Data, 1993, 22 (1), pg. 113-262; Lever, A. P. B., must be longer at a lower light intensity than at a higher Licoccia, S., Magnell, K., Minor, P. C., Ramaswamy, B. S., intensity. In general, depending on the field of use, exposure Adv. Chem. Ser, 1982, 201, pg. 237-52; West, M.A., Creat. time of a few minutes up to a few hours is possible. Detect. Excited State, 1976, 4, pg. 217-307; Ford, W. E., If the process is carried out in an aqueous medium (for Rihter, B. D., Kenney, M. E., Rodgers, M. A. J., Photochem. 45 example the sterilization of textiles), the irradiation with PhotobioL, 1989, 50 (3), pg. 277–282; Firey, P.A., Ford, W. light can either be carried out directly in the treatment E., Sounik, J. R., Kenney, M. E., Rodgers, A. J. R., J. Am. medium, by means of an artificial Source of light mounted Chem. Soc., 1988, 110, pg. 7626–7630; Firey, P. A., inside or outside the medium, or the articles, in a moist State, Rodgers, M. A. J., Photochem. Photobiol., 1987, 45 (4), pg. can Subsequently either be irradiated, again by means of an 535-8; all of which are incorporated by reference in their 50 artificial Source of light, or can be exposed to Sunlight. Good entirety. antimicrobial effects con be achieved even with very low For the purposes of the present invention the delta triplet concentrations of active Substance, for example at 0.001 yield is determined by determining the % quantum yield of ppm. Depending on the field of use and on the phthalocya triplet fro the phthalocyanine or naphthalocyanine of interest nine or naphthylocyanine derivative employed, a concentra and this is the term (p. The % quantum yield of 55 tion between 0.005 and 2000, preferably 0.01 and 1000 ppm triplet for the phthalocyanine or naphthalocyanine prior to is preferable. introduction of the Substituent is determine. This value is The methods of the present invention can also be accom (p. The value are place in the following equation plished in Solvent based carriers or in low aqueous Solutions. For the purpose of the present invention the term low triplet state quantum yield increase=A(P=(Pists 60 aqueous means that water is added to a carrier System to Prip-reference modify the properties of the carrier and not solely for the When the value for Ap, is a number greater than or equal purpose of Solublizing the Substrate. For example, Solvents to 1, the Substitution made therein for a hydrogen atom on that are capable of holding Solublized oxygen as well as the (Sens.) unit of the photosensitizer is a preferred embodi forming a miscible System with water are preferred. Non ments of the present invention. 65 limiting examples of these Solvents are butoxy propoxy In particular, the present invention relates to proceSS for propanol (BPP), methoxy propoxy propanol (MPP), ethoxy bleaching or removing Stains from textiles, organic or inor propoxy propanol (EPP), and propoxy propoxy propanol US 6,417,150 B2 25 26 (PPP). Embodiments of the present invention which com limited to these examples or combinations thereof. The prise these non-classical aqueous compositions are most builders are present from about 0% to about 50%, preferably useful when the photobleach must be applied to a woven from about 5% to about 30%, by weight of the composition. fabric or Surface that contains agents which repel water and The hard Surface cleaner of the present invention option moisture. ally contains builders, examples of which are, Silicates, The Sterilization of textiles of Synthetic or natural original carbonates, and Zeolites, however the user is not limited to may be mentioned as an important application. Thus, mate these examples or combinations thereof. The builders are rial to be washed in the household or in industry can be present from about 0% to about 50%, preferably from about disinfected by means of the methods of the present inven 5% to about 30%, by weight of the composition. tion. The material to be washed can be treated for this The hard Surface cleaner of the present invention option purpose in the manner mentioned above with aqueous ally contains abrasives from about 0.5% to about 85%, Solutions of the phthalocyanines or naphthalocyanines of the preferably from about 10% to about 85%, by weight of the present invention while being irradiated with light. The composition. Suitable abrasives are Silicates, carbonates, phthalocyanine and naphthalocyanines can advantageously perlite, clay, and pulverized ceramic clay, however, the user be present in the treatment medium in a concentration of 15 is not restricted to these examples or combinations thereof. from 0.01 to about 2000 mg per liter, preferably from 0.1 to Substances which increase the action can also be added in 1000, more preferably from 1 to 500. The sterilization can the process according to the invention, interalia electrolytes, be carried out advantageously together with the Washing for example inorganic Salts, for instance Sodium chloride, process. For this purpose, the material to be washed is potassium chloride, Sodium Sulfate, potassium Sulfate, treated with a wash medium containing customary detergent Sodium acetate ammonium acetate, alkali metal phosphates Substances, one or more phthalocyanines or naphthalocya and alkali metal tri-polyphosphates, especially Sodium chlo nines according to the present invention and, if desired, ride and Sodium sulfate. These salts can be added to the inorganic Salts and/or other adjunct materials having anti agents according to the invention or can be added directly in microbial properties. The Washing process con be carried out the application method, So that they are present in the manually, for example in a tub, or can be carried out in a 25 application Solution in a concentration of, preferably 0.1 to Washing machine. The necessary exposure to light can be 10%, by weight. effected during the Washing process by means of Suitable What is meant by the term acqueous Solution is a Solution light Sources, or the moist material being washed can also, that is essentially water, however the formulator may Subsequently, for example during drying, either be exposed include adjunct materials as well as a Surfactant to aid in to a Suitable artificial Source of light or simply exposed to removal of the “treated micro organisms during rinsing or Sunlight, for example line drying. Subsequent cleaning. The presence of an aqueous Solution Surface bleaching can be achieved, for example by apply facilitates the production of Singlet oxygen due to the higher ing to the appropriate Surface, an aqueous Solution of the concentration of OXygen in Water than in air. phthalocyanine or naphthalocyanine compound according to Surfactant the present invention, this Solution preferably comprising 35 The instant cleaning compositions contain from about from about 0.001 to about 10%, by weight of active sub 0.1% to about 60% by weight of a surfactant selected from stance. The Solution can also comprise, in addition, other the group consisting of anionic, nonionic, ampholytic and customary additives, for example wetting agents, dispersing Zwitterinonic Surface active agents. For liquid Systems, agents or emulsifiers, detergent Substances and, if desired Surfactant is preferably present to the extent of from about inorganic Salts. After this Solution has been applied, the 40 0.1% to 20% by weight of the composition. For solid (i.e. Surface is simply exposed to Sunlight or, if required, it can granular) and Viscous Semi-Solid (i.e. gelatinous, pastes, in addition be irradiated by means of an artificial Source of etc.) Systems, Surfactant is preferably present to the extent of light. It is advisable to keep the Surface moist during the from about 1.5% to 30% by weight of the composition. exposure to light. Nonlimiting examples of Surfactants useful herein typi The laundry compositions of the present invention option 45 cally at levels from about 1% to about 55%, by weight, ally comprise detersive Surfactants, examples of which are, include the conventional C-C alkylbenzene Sulfonates anionic, cationic, nonionic, amphoteric and Zwitterionic, (“LAS) and primary, branched-chain and random Co-Co however the formulator is not limited to these examples or alkyl Sulfates (“AS”), the Co-Cs. Secondary (2.3) alkyl combinations thereof. The Surfactants are present from sulfates of the formula CH-(CH2)(CHOSOM)CH and about 0% to about 95%, preferably from about 5% to about 50 CH, (CH),(CHOSOM)CHCH, where x and (y+1) are 30%, by weight of the composition. integers of at least about 7, preferably at least about 9, and The cleaning compositions of the present invention M is a water-Solubilizing cation, especially Sodium, unsat optionally comprise detersive Surfactants, examples of urated Sulfates Such as oleyl Sulfate, the Co-Cs alkyl which are, anionic, cationic, nonionic, amphoteric and alkoxy sulfates (“AES”; especially E.O. 1-7 ethoxy Zwitterionic, however the formulator is not limited to these 55 Sulfates), Co-Cs alkyl alkoxy carboxylates (especially the examples or combinations thereof. The Surfactants are EO 1-5 ethoxycarboxylates), the Co-Cs glycerol ethers, present from about 0% to about 50%, preferably from about the Co-Cs alkyl polyglycosides and their corresponding 5% to about 30%, by weight of the composition. Sulfated polyglycosides, and C-C alpha-Sulfonated fatty The laundry compositions of the present invention option acid esters. If desired, the conventional nonionic and ampho ally contains builders, examples of which are, Silicates, 60 teric Surfactants Such as the C-C alkyl ethoxylates carbonates, and Zeolites, however the user is not limited to ("AE') including the So-called narrow peaked alkyl ethoxy these examples or combinations thereof. The builders are lates and C-C alkyl phenol alkoxylates (especially present from about 0% to about 50%, preferably from about ethoxylates and mixed ethoxy/propoxy), C-C betaines 5% to about 30%, by weight of the composition. and Sulfobetaines ("Sultaines”), Co-Cs amine oxides, and The cleaning compositions of the present invention 65 the like, can also be included in the Overall compositions. optionally contains builders, examples of which are, The Co-Cs N-alkyl polyhydroxy fatty acid anides can also Silicates, carbonates, and Zeolites, however the user is not be used. Typical examples include the C-Cls US 6,417,150 B2 27 28 N-methylglucamides. See WO 9,206,154. Other Sugar Synthesis using alpha olefins and Sulfuric acid is disclosed in derived surfactants include the N-alkoxy polyhydroxy fatty U.S. Pat. No. 3,234,258, Morris, issued Feb. 8, 1966 or in acid amides, Such as Co-Cs. N-(3-methoxypropyl)gluca U.S. Pat. No. 5,075,041, Lutz, issued Dec. 24, 1991. The mide. The N-propyl through N-hexyl C-Cls glucamides Synthesis conducted in Solvents which afford the Secondary can be used for low Sudsing. Co-Co conventional Soaps (2.3) alkyl Sulfates on cooling, yields products which, when may also be used. If high Sudsing is desired, the branched purified to remove the unreacted materials, randomly Sul chain Co-C soaps may be used. Mixtures of anionic and fated materials, unsulfated by-products Such as C10 and nonionic Surfactants are especially useful. Other conven higher alcohols, Secondary olefin Sulfonates, and the like, tional useful Surfactants are described further herein and are are typically 90+% pure mixtures of 2- and 3-sulfated listed in Standard texts. materials (Some Sodium Sulfate may be present) and are Anionic Surfactants can be broadly described as the white, non tacky, apparently crystalline, Solids. Some 2,3- water-Soluble Salts, particularly the alkali metal Salts, of disulfates may also be present, but generally comprise no organic Sulfuric reaction products having in their molecular more than 5% of the mixture of secondary (2.3) alkyl Structure an alkyl radical containing from about 8 to about mono-Sulfates. Such materials are available as under the 22 carbon atoms and a radical Selected from the group 15 consisting of Sulfonic acid and Sulfuric acid ester radicals. name “DAN", e.g., “DAN 200” from Shell Oil Company. (Included in the term alkyl is the alkyl portion of higher acyl Bleaching Agents and Bleach Activators radicals.) Important examples of the anionic Synthetic deter The detergent compositions herein may optionally con gents which can form the Surfactant component of the tain bleaching agents or bleaching compositions containing compositions of the present invention are the Sodium or a bleaching agent and one or more bleach activators. When potassium alkyl Sulfates, especially those obtained by Sul present, bleaching agents will typically be at levels of from fating the higher alcohols (C8-18 carbon atoms) produced about 1% to about 30%, more typically from about 5% to by reducing the glycerides of tallow or coconut oil; Sodium about 20%, of the detergent composition, especially for or potassium alkyl benzene Sulfonates, in which the alkyl fabric laundering. If present, the amount of bleach activators group contains from about 9 to about 15 carbon atoms, (the 25 alkyl radical can be a straight or branched aliphatic chain); will typically be from about 0.1% to about 60%, more Sodium alkyl glyceryl ether Sulfonates, especially those typically from about 0.5% to about 40% of the bleaching ethers of the higher alcohols derived from tallow and composition comprising the bleaching agent-plus-bleach coconut oil; Sodium coconut oil fatty acid monoglyceride activator. Sulfates and Sulfonates, Sodium or potassium Salts of Sulfuric The bleaching agents used herein can be any of the acid ester of the reaction product of one mole of a higher bleaching agents useful for detergent compositions in textile fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to cleaning, hard Surface cleaning, or other cleaning purposes about 10 moles of ethylene oxide, Sodium or potassium Salts that are now known or become known. These include of alkyl phenol ethylene oxide ether sulfates with about 1 to oxygen bleaches other than the hypohalite (e.g. about 10 units of ethylene oxide per molecule and in which 35 hypochlorite) bleaches. Perborate (e.g., mono- or tetra the alkyl radicals contain from 8 to 12 carbon atoms, the hydrate Sodium salts) and percarbonate bleaches can be used reaction products of fatty acids are derived from coconut oil herein. Sodium or potassium Salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived Another category of bleaching agent that can be used from coconut oil and Sodium or potassium beta-acetoxy- or 40 without restriction encompasses percarboxylic acid bleach beta-acetamido-alkaneSulfonates where the alkane has from ing agents and Salts thereof. Suitable examples of this class 8 to 22 carbon atoms. of agents include magnesium monoperoxyphthalate Additionally, Secondary alkyl Sulfates may be used by the hexahydrate, the magnesium Salt of metachloro perbenzoic formulator exclusively or in conjunction with other Surfac acid, 4-nonylamino-4-OXOperoxybutyric acid and diperoxy tant materials and the following identifies and illustrates the 45 dodecanedioic acid. Such bleaching agents are disclosed in differences between Sulfated Surfactants and otherwise con U.S. Pat. No. 4.483,781, Hartman, issued Nov. 20, 1984. ventional alkyl Sulfate Surfactants. Non-limiting examples of U.S. patent application Ser. No. 740,446, Burns et al, filed Such ingredients are as follows. Jun. 3, 1985, European Patent Application 0,133,354, Banks Conventional primary alkyl Sulfates (LAS), Such as those et al, published Feb. 20, 1985, and U.S. Pat. No. 4,412,934. illustrated above, have the general formula ROSO3-M+ 50 Chung et al., issued Nov. 1, 1983. Highly preferred bleaching wherein R is typically a linear C8-22 hydrocarbyl group and agents also include 6-nonylamino-6-OXOperoxycaproic acid M is a water Solublizing cation, for example Sodium LAS. as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 Branched chain primary alkyl Sulfate Surfactants (i.e., to Burns et al. branched-chain “PAS”) having 8-20 carbon atoms are also Peroxygen bleaching agents can also be used. Suitable know; see, for example, Eur. Pat. Appl. 439,316, Smith et 55 al., filed Jan. 21, 1991. peroxygen bleaching compounds include Sodium carbonate Conventional Secondary alkyl Sulfate Surfactants are those peroxyhydrate and equivalent "percarbonate' bleaches, materials which have the sulfate moiety distributed ran Sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, domly along the hydrocarbyl “backbone' of the molecule. and sodium peroxide. Persulfate bleach (e.g., OXONE, Such materials may be depicted by the Structure 60 manufactured commercially by DuPont) can also be used. A preferred percarbonate bleach comprises dry particles CH(CH2)(CHOSOM)(CH2)CH, having an average particle size in the range from about 500 wherein m and n are integers of 2 of greater and the Sum of micrometers to about 1,000 micrometers, not more than m+n is typically about 9 to 17, and M is a water-solublizing about 10% by weight of said particles being smaller than cation. 65 about 200 micrometers and not more than about 10% by The aforementioned Secondary alkyl Sulfates are those weight of Said particles being larger than about 1,250 prepared by the addition of HSO to olefins. A typical micrometers. Optionally, the percarbonate can be coated US 6,417,150 B2 29 30 with silicate, borate or water-soluble Surfactants. Percarbon Valerolactam, 3,5,5-trimethylhexanoyl Valerolactam and ate is available from various commercial Sources Such as mixtures thereof. See also U.S. Pat. No. 4,545,784, issued to FMC, Solvay and Tokai Denka. Sanderson, Oct. 8, 1985, incorporated herein by reference, Mixtures of bleaching agents can also be used. which discloses acyl caprolactams, including benzoyl Peroxygen bleaching agents, the perborates, the caprolactam, adsorbed into Sodium perborate. percarbonates, etc., are preferably combined with bleach AS a practical matter, and not by way of limitation, the activators, which lead to the in Situ production in aqueous compositions and processes herein can be adjusted to pro Solution (i.e., during the washing process) of the peroxy acid vide on the order of at least one part per ten million of the corresponding to the bleach activator. Various nonlimiting active bleach catalyst Species in the aqueous washing liquor, examples of activators are disclosed in U.S. Pat. No. 4,915, 1O and will preferably provide from about 0.1 ppm to about 700 854, issued Apr. 10, 1990 to Mao et al, and U.S. Pat. No. ppm, more preferably from about 1 ppm to about 500 ppm, 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and of the catalyst Species in the laundry liquor. tetraacetyl ethylene diamine (TAED) activators are typical, Bleaching agents other than oxygen bleaching agents are and mixtures thereof can also be used. See also U.S. Pat. No. also known in the art and can be utilized herein. One type of 4,634,551 for other typical bleaches and activators useful 15 non-oxygen bleaching agent of particular interest includes herein. photoactivated bleaching agents Such as the Sulfonated Zinc Highly preferred amido-derived bleach activators are and/or aluminum phthalocyanines. See U.S. Pat. No. 4,033, those of the formulae: 718, issued Jul. 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of Such bleaches, especially Sul wherein R is an alkyl group containing from about 6 to fonate Zinc phthalocyanine. about 12 carbon atoms, R is an alkylene containing from 1 Buffers to about 6 carbon atoms, R is H or alkyl, aryl, or alkaryl Buffers can be included in the formulations herein for a containing from about 1 to about 10 carbon atoms, and L is variety of purposes. One Such purpose is to adjust the any Suitable leaving group. A leaving group is any group that 25 cleaning Surface pH to optimize the hard Surface cleaner is displaced from the bleach activator as a consequence of composition effectiveneSS relative to a particular type of Soil the nucleophilic attack on the bleach activator by the per or stain. Buffers may be included to stabilize the adjunct hydrolysis anion. A preferred leaving group is phenyl Sul ingredients with respect to extended shelf life or for the fonate. purpose of maintaining compatibility between various aes Preferred examples of bleach activators of the above thetic ingredients. The hard Surface cleaner of the present formulae include (6 - octan amido-cap royl) invention optionally contains buffers to adjust the pH in a oxybenzene Sulfonate, (6 - no na namido cap royl) range from about 7 to about 13, preferably from about 8 to oxybenzene Sulfonate, (6-decanamido-cap royl) about 13, more preferably from about 10 to about 11. oxybenzeneSulfonate, and mixtures thereof as described in Non-limiting examples of Such Suitable buffers are potas U.S. Pat. No. 4,634,551, incorporated herein by reference. 35 sium carbonate, Sodium carbonate, and Sodium bicarbonate, Another class of bleach activators comprises the however, the formulator is not restricted to these examples benzoxazin-type activators disclosed by Hodge et al in U.S. or combinations thereof. Pat. No. 4,966,723, issued Oct. 30, 1990, incorporated herein by reference. A highly preferred activator of the Adjunct Materials benzoxazin-type is: 40 The compositions herein can optionally include one or more other detergent adjunct materials or other materials for O assisting or enhancing cleaning performance, treatment of the Surface to be cleaned, or to modify the aesthetics of the C composition (e.g., perfumes, colorants, dyes, etc.). The 45 following are illustrative examples of Such adjunct materials C but are not meant to be exclusive or limiting in Scope. y4. O Chelating Agents The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Still another class of preferred bleach activators includes 50 Such chelating agents can be Selected from the group the acyl lactam activators, especially acyl caprolactams and consisting of amino carboxylates, amino phosphonates, acyl Valerolactams of the formulae: polyfunctionally-Substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intend ing to be bound by theory, it is believed that the benefit of O C-CH-CH O C-CH-CH 55 these materials is due in part to their exceptional ability to | V | remove iron and manganese ions from Washing Solutions by R-C-N y H. R-C-N formation of Soluble chelates. Amino carboxylates useful as optional chelating agents CH2 CH2 CH2 CH2 include ethylene diamine tetrace tate S, 60 N-hydroxyethylethylene diamine triacetates, nitrilo wherein R is H or an alkyl, aryl, alkoxyaryl, or alkaryl triacetate S, ethylene diamine tetraproprio nates, group containing from 1 to about 12 carbon atoms. Highly trie thylene tetra a mine he Xa c e tate S, preferred lactam activators include benzoyl caprolactam, diethylenetriaminepentaacetates, and ethanoldiglycines, octanoyl caprolactam,3,5,5-trimethylhexanoyl caprolactam, alkali metal, ammonium, and Substituted ammonium Salts nonanoyl caprolactam, decanoyl caprolactam, undecenoyl 65 therein and mixtures therein. caprolactam, benzoyl Valerolactam, octanoyl Valerolactam, Amino phosphonates are also Suitable for use as chelating decanoyl Valerolactam, undecenoyl Valerolactam, nonanoyl agents in the compositions of the invention when at lease US 6,417,150 B2 31 32 low levels of total phosphorus are permitted in detergent It has been discovered that abrasive compositions of this compositions, and include ethylene diaminetetrakis desired type can be realized by utilizing a particular type of (methylenephosphonates) as DEQUEST, Preferred, these expanded perlite abrasive in combination with the amino phosphonates to not contain alkyl or alkenyl groups Surfactants, filler material, and other optional Scouring mate with more than about 6 carbon atoms. rial ingredients listed herein. The abrasive materials Suitable Polyfunctionally-Substituted aromatic chelating agents to the present invention are those contained in U.S. Pat. No. are also useful in the compositions herein. See U.S. Pat. No. 4,051,056, Hartman, issued Sep. 27, 1977 and included herein by reference. 3.812,044, issued May 21, 1974, to Connor et al. Preferred Perfumes compounds of this type in acid form are dihydroxydisul Perfumes are an important ingredient especially for the fobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. 1O liquid composition embodiment. Perfume is usually used at A preferred biodegradable chelator for use herein is levels of from 0% to 5%. In U.S. Pat. No. 4,246,129, Kacher, ethylenediamine disuccinate (“EDDS”), especially the S.S issued Jan. 20, 1981 (incorporated herein by reference), isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, certain perfume materials are disclosed which perform the 1987, to Hartman and Perkins. added function reducing the Solubility of anionic Sulfonate If utilized, these chelating agents will generally comprise 15 and Sulfate Surfactants. from about 0.1% to about 10% by weight of the detergent Dves compositions herein. More preferably, if utilized, the chelat ises may be include at levels of from abut 0.5% to 12%, ing agents will comprise from about 0.1% to about 3.0% by preferably 1.5% to 5%. Solids and viscous semi-solids can weight of Such compositions be made with 1.5% dye and no perfume. Examples of Inert Salts suitable dyes are Alizarine Light Blue B (C.I. 63010), Carta The inert salts (filler salts) used in the compositions of the Blue VP (C.I. 24.401), Acid Green 2C (C.I. 42085), Astrogen present invention can be any water-Soluble inorganic or Green D (C.I. 42040), Supranol Cyanine 7B (C.I. 42675, organic Salt or mixtures of Such Salts which do not destabi Maxilon Blue 3RL (C.I. Basic Blue 80), Drimarine Blue lize the Surfactant. For the purposed of the present invention, Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL “water-soluble” means having a solubility in water of at least 25 (C.I. Acid Blue 182), FD&C Blue No. 1 and FD&C Green 1 gram per 100 grams of water at 20° C. Examples of No. 3. (See the patents of Kitko, U.S. Pat. No. 4,248,827 Suitable Salts include various alkali metal and/or alkali earth issued Feb. 3, 1981 and U.S. Pat. No. 4,200,606, issued Apr. metal Sulfate, chlorides, borates, bromides, fluorides, 29, 1980, both incorporated herein by reference.) C.I. refers phosphates, carbonates, bicarbonates, citrates, acetates, to Color Index. lactates, etc. Optional Adjuncts Ingredients Specific examples of Suitable Salts include Sodium Sulfate, AS a preferred embodiment, the conventional adjunct Sodium chloride, potassium chloride, Sodium carbonate, ingredients employed herein can be selected from typical potassium Sulfate, lithium chloride, lithium Sulfate, tripotas components such as enzymes (compatible with the appli sium phosphate, Sodium borate, potassium bromide, potas cable with other adjunct ingredients), especially proteases, sium fluoride, Sodium bicarbonate, magnesium Sulfate, mag 35 lipases, cellulases, color Speckles, Suds boosters, Suds nesium chloride, Sodium citrate, Sodium acetate, magnesium SupreSSors, anti-tarnish and/or anti-corrosion agents, Soil lactate, Sodium fluoride. The preferred Salts are inorganic Suspending agents, germicides, alkalinity Sources, Salts preferably the alkali metal Sulfates and chlorides. hydrotropes, anti-oxidants, enzyme Stabilizing agents, Particularly preferred salts, because of their low cost are Solvents, clay Soil chelating agents will generally comprise Sodium Sulfate and Sodium chloride. The Salts are present in 40 from about 0.1% to about 10% by weight of the detergent the compositions at levels of from 0% to 40%, preferably compositions herein. More preferably, if utilized. the chelat 10% to 20%. ing agents will comprise from about 0.1% to about 3.0% by Abrasives weight of Such composition removal/anti-redeposition An essential component of many Solid or Viscous Semi agents, polymeric dispersing agents, dye transfer inhibiting Solid hard Surface cleaning compositions is the abrasive 45 agents, including polyamine N-oxides Such as polyvinylpyr material added to facilitate the action of Scouring. Abrasive rolidone and copolymers of N-vinyl imidazole and N-vinyl Scouring cleansers provide a convenient and useful means pyrrollidone, etc. for carrying out the Sanitizing of porcelain and tile Surfaces, EXAMPLE 1. especially tubs, showers and toilet bowls. The particulate Preparation of Dilithium Naphthalocyanine abrasive material within Such compositions Serves to abrade 50 and loosen Soil adhering to hard Surfaces and further Serves To a refluxing Solution of 2,3-dicyanonaphthalene (10g, to create more intimate contact between hard Surface Stain 56.1 mmole) in anhydrous 1-butanol (300 mL) is added and the Surfactant and/or bleaching agents also present in the lithium shot (1.56 g, 224.5 mmole). The solution is refluxed cleansing compositions. 6 hours under argon, diluted with 500 mL methanol and allowed to crystallize in the cold at about 0°C. for 18 hours. Abrasive cleaners have traditionally contained water 55 The resulting green Solid is recovered by filtration, dried in insoluble, relatively hard, particulate mineral material as the vacuo at 80 C. and used without further purification. abrasive agent. The most common Such abrasive agent is The above procedure is Suitable for preparing 1,4,8,11, finely divided Silica Sand having particle size varying 15,18,22,25-octabutoxy-29,31 -dilithium phthalocyanine between about 1 and 300 microns and specific gravity of from 3,6-dibutoxyphthalonitrile; 2,3,9,10,16,17,23,24 about 2.1 or higher. While such material is generally very 60 octachloro-29,31-dilithium phthalocyanine from 4,5- effective in Scouring Soil and Stains from the Surfaces being dichlorophthalonitrile; and tetrabutoxy-29,31-dilithium treated, abrasive material of this type tends to be difficult to rinse away from the toilet bowl, shower or bathtub surface. phthalcyanine from 3-butoxyphthalonitrile. In the case where moderate or highly water Soluble EXAMPLE 2 abrasive material is required (i.e. Sodium carbonate) imido 65 Preparation of Naphthalocyanine disulfate can be used as the Sole abrasive or otherwise added To a solution of dilithium naphthalocyanine (2 g, 2.75 in part. mmole) in DMF (200 ml) is added 1N HCl (10 mL). The US 6,417,150 B2 33 34 Solution is stirred at room temperature of approximately 1 The above procedure is Suitable for use in preparing hour. The Solution is then diluted with 200 mL of water over 1,4,8,11,15,18,22,25-octabutoxy germanium(IV) a period of about 30 minutes. The green solid which results phthalocyanine-di-(glycerol-di-(diethylene glycol methyl is collected by filtration and dried in vacuo at 100° C. and ether)); 1,4,8,11,15,18,22,25-octabutoxy germanium(IV) used without further purification. phthalocyanine-di-(Neodol 23-6.5); tetrabutoxy tin(IV) The above procedure is Suitable for preparing 1,4,8,11, phthalcyanine-di-(poly(ethylene glycol 350) methyl ether); 15,18,22,25-octabutoxy-29H,31H-phthalocyanine; 2,3,9,10, tetrabutoxy tin(IV) phthalcyanine-di-(glycerol-di 16, 17,23,24-octachloro-29H,31H-phthalocyanine; and (diethylene glycol methyl ether)); and tetrabutoxy tin(IV) tetrabutoxy-29H,31H-phthalcyanine. phthalcyanine-di-(Neodol 23-6.5). 1O EXAMPLE 3 EXAMPLE 7 Preparation of Tin(IV) Naphthalocyanine Dichloride Preparation of 1,4,8,11,15,18,22,25-octabutoxy Germanium A mixture of naphthalocyanine (0.2g, 0.28 mmole), tin (IV) Phthalocyanine-di-(Triethanol Amine Dimethyl Sulfate tetrachloride pentahydrate (0.456 g, 1.3 mmole) in DMF is Quat.) refluxed for one hour under argon then allowed to cool. The 15 A mixture of 1,4,8,11,15,18,22,25-octabutoxy germanium green Solid that results is filtered off, dired in vacuo, and (IV) phthalocyanine dihydroxide (0.5 g., 0.405 mmole), used without further purification. anhydrous triethanolamine (10g, 67.04 mmole) and xylene The above procedure is Suitable for preparing 1,4,8,11, (175 mL) is slowly heated to reflux over a period of 1.5 15,18,22,25-octabutoxy tin(IV) phthalocyanine dichloride; hours. The reaction flask is fitted with a Dean-Stark trap and 2,3,9,10,16,17,23,24-octachloro tin(IV) phthalocanine the water is removed by azeotropic distillation. After 2 hours dichloride; and tetrabutoxy tin(IV) phthalcyanine dichlo the Solution is cooled, and the Solvent is removed in vacuo. ride. The resulting oil is dissolved in 50 mL DMF and slowly EXAMPLE 4 added to 800 mL of water over 0.5 hour. The blue Solid Preparation of Germanium(IV) Naphthalocyanine Dichlo which results is collected by filtration and dried under ride 25 vacuum at 80° C. This solid product is added to a dioxane To a refluxing solution of naphthalocyanine (0.20 g, 0.28 (100 mL) which contains dimethylsulfate (0.15 g, 1.215 mmole), germanium tetrachloride (0.15 mL) in anhydrous mmole). The resulting blue solid is collected by filtration, DMF (20 mL) under argon, is added in portions over a dried and used without further purification. period of 5 hours additional germanium tetrachloride (0.25 The above procedure is Suitable for use in preparing mL). The solution is cooled, diluted with dichloromethane tetrabutoxy tin(IV) phthalcyanine-di-(triethanolamine dim 940 mL), extracted twice with 30 mL portions of 10% ethyl Sulfate quat). hydrochloric acid, then three times with 30 mL portions of The cleaning compositions provided in accordance with distilled water, died over MgSO, filtered and concentrated this invention may be in the form of granules, liquids, bars, to yield a green Solid that is used without further purifica and the like, and typically are formulated to provide an tion. 35 in-use pH in the range of 9 to 11, however in the case of The above procedure is Suitable for preparing 1,4,8,11, non-aqueous or low aqueous compositions the pH ranges 15,18,22,25-octabutoxy germanium(IV) phthalocyanine may vary outside this range. Various carrierS Such as Sodium dichloride; 2,3,9,10,16,1723,24-octachloro germanium(IV) Sulfate, water, water-ethanol, BPP, MPP, EPP, PPP, sodium phthalocyanine dichloride; and tetrabutoxy germanium(IV) carbonate, and the like, may be used routinely to formulate phthalcyanine dichloride. 40 the finished products. Granules may be produced by Spray drying or by agglomeration, using known techniques, to EXAMPLE 5 provide products in the density range of 350-950 g/l. Bars Preparation of 1,4,8,11,15,18,22,25-octabutoxy Platinum may be formulated using conventional extrusion techniques. (IV) Dichloride The photobleach-chelant may be pre-formed, if desired. The To a refluxing solution of 1,4,8,11,15,18,22,25 45 compositions may also contain conventional perfumes, Octabutoxyphthalocyanine (0.20 g, 0.18 mmole), Platinum bactericides, hydrotropes and the like. In the case of non Tetrachloride (0.15 ml) in 20 ml anhydrous N,N- aqueous or low aqueous compositions, the cleaning compo Dimethylformamide under argon over a five hour period is Sitions may be applied to an article which is used to deliver added in five portions Platinum Tetrachloride (0.25 ml). The the compositions of the present invention to a fabric or to a Solution is cooled, diluted with 40 ml Dichloromethane, 50 hard Surface. Non-limiting examples of compositions extracted 2x30 ml 10% hydrochloric acid, 3x30 ml distilled water, dried over anhydrous Magnesium Sulfate and according to this invention are as follows: Stripped of Solvent yielding a green Solid which is used EXAMPLES 8-11 without further purification. EXAMPLE 6 55 Preparation of 1,4,8,11,15,18,22,25-octabutoxy Germanium (IV) Phthalocyaninedi-(poly(ethylene glycol 350) Methyl Weight % Ether) Ingredients 8 9 1O 11 A mixture of 1,48,11,15,18,22,25-Octabutoxy germanium Sodium linear alkylbenzene 15 3O 2O 25 (IV) phthalocyanine dihydroxide (1.0 g, 0.81 mmole), poly 60 Sulfonate (ethylene glycol 350) methyl ether (22.68 g, 64.8 mmole) NEODOL 1. 1. 1. 1. and xylene (175 mL) is slowly heated to reflux under argon Alkyl dimethyl ammonium 0.5 1. 0.5 O.7 chloride over a period of 3 hours. The reaction flask is fitted with a Sodium tripolyphosphate 15 35 22 28 Dean-Stark trap and the water is removed by azeotropic Sodium carbonate 1O 1O 15 15 distillation. After 48 hours the reaction is cooled, the solvent 65 SOKALAN 2 2 2 2 removed in vacuo and the crude product is used without Carboxymethylcellulose 1. 1. 1. 1. further purification. US 6,417,150 B2 35 36

-continued -continued Weight % Ingredients Weight % Ingredients 8 9 1O 11 Carboxymethylcellulose O.2 Polyacrylate (m.w. 1400) O.2 Tinopal CBS-X O.1 O1 O1 O.1 Sodium percarbonate 15 Soil release agent' O.2 O.2 O.3 O.3 Protease O.3 Savinase 6.0T O.3 O6 0.5 O.6 CaSO 1. Ban 3OOT O.2 0.5 0.5 O.6 MgSO 1. Lipolase 100T O.1 O.2 O.2 O.3 1O Photobleach'(ppm) O.O1 CAREZYMEST O.1 O.2 O.2 O.3 Minors/fillers balance Sodium perborate 3 5 Nonanoyloxybenzenesulfonate 2 3 "Photobleach germanium(IV) octabutoxyphthalocyanine-di-(Neodol 23-6.5) Photobleach (ppm) O.OOS 0.01 - Photobleach (ppm) O.OO8 O.O1 Minors/fillers balance balance balance balance 15 "Soil release polymer according to U.S. Pat. No. 4.968,451 Scheibel et al. *Photobleach germanium(IV)octabutoxyphthalocyanine poly(ethylene Low Aqueous Cleaning Composition glycol 350) according to Example 6 Photobleach tin(IV)octabutoxyphthalocyanine poly(ethylene glycol 350) according to Example 6 EXAMPLE 1.7 EXAMPLES 12-15

25 Ingredients Weight % Weight % Photobleach 0.005-1.5 Ingredients 12 13 14 15 BPP2 5-25 1,2-octanediol O.1-70 C-C alkyl sulfate 6 6 8 7 Magnesium alkylethoxy (E1) sulfate O.O1-08 C-C alkyl ethoxylate (EO 4.2) 11 12 1O 5 Magnesium alkylethoxy (E6.5) sulfate O.O1-08 Zeolite 38 35 3O 1O C2 dimethylamine oxide O.O1-08 Trisodium citrate 2 PEMULEN 0.05-0.2 SKS-6 silicate builder 1O Perfume 0.01-1.5 Acrylate/maleate copolymer 4 Water balance Sodium carbonate 9 1O 4 5 EDTMP O.2 O.3 "Photobleach germanium(IV) octabutoxyphthalocyanine diglycerol-di Ethylenediamine disuccinate 0.4 35 (siethylene glycol methyl ether). Sodium percarbonate 8 1O 25 Other co-solvents which can be used herein together with the BPP, MPP, Nonanolyoxybenzene sulfonate 3 EPP and PPP primary solvents include various glycol ethers, including Tetraacetylethylenediamine 7 materials marketed under trademarks such as Carbitol, methyl Carbitol, Savinase (4.0 KNPU/g) 2 1.5 2 1.5 butyl Carbitol, propyl Carbitol, hexyl Cellosolve, and the like. If desired, Lipolase (100,000 LU/g) O.2 0.5 0.5 and having due regard for safety and odor for in-home use, various 40 conventional chlorinated and hydrocarbon dry cleaning solvents may also Soap 1. be used. Included among these are 1,2-dichloroethane, trichloroethylene, Suds suppressor 2 2 2 2 isoparaffins, and mixtures thereof. Soil release agent’ 0.5 0.5 As disclosed in U.S. Pat. Nos. 4,758,641 and 5,004,557, such Soil release agent 0.5 0.5 0.5 polyacrylates include homopolymers which may be crosslinked to varying Dispersent 2.5 - degrees, as well as non-crosslinked. Preferred herein are homopolymers Photobleach (ppm) O.OOS 0.01 - having a molecular weight in the range of from about 100,000 to about Photobleach'(ppm) O.OO8 O.O1 45 Minors/fillers balance balance balance balance 10,000,000, preferably 2000,000 to 5,000,000. 'Ethylenediamine tetramethylenephosphonate °Soil release polymer according to U.S. Pat. No. 5,415,807, Gosselink et al. issued May 16, 1995. Soil release polymer according to U.S. Pat. No. 4,702,857, Gosselink For the materials disclosed in Example 29, excellent 50 cleaning performance is Secured using any non-immersion issued"Hydrophobic October soil 27, dispersant1987. according to U.S. Pat. No. 5,565,145, processes and articles to provide from about 5 g to about 50 WatsonPhotobleach et al. germanium(IV)issued October 15,octabutoxyphthalocyanine 1996. according to g of the cleaning compositions per kilogram of fabric being Example 7. cleaned. Use of the polyacrylate emulsifier at the indicated Photobleach tin(IV) tetrabutoxyphthalocyanine according to Example 7. low levels minimizes residues on the fabrics. 55 EXAMPLE 16 Fabrics are laundered using the foregoing compositions, typically at usage concentrations of from about 10 ppm to about 10,000 ppm. The fabrics are dried in the presence of 60 light, preferably natural Sunlight, to achieve improved pho Ingredients Weight % tobleaching benefits. C. Linear alkyl benzene Sulphonate 3O Phosphate (as sodium tripolyphosphate) 7 Sodium carbonate 15 What is claimed is: Sodium pyrophosphate 7 Coconut monoethanolamide 2 65 1. A photochemical Singlet oxygen generator having a Zeolite A 5 Q-band maximum absorption wavelength of 660 nanom eters or greater, having the formula: US 6,417,150 B2 37 38 -continued 27, r. -O-CH CH-(O)(CH2)(OCH2CH2); Z.

y—NN wherein Z is hydrogen, hydroxyl, C-C alkyl, N Rii II M-sR N C-C alkoxy, -COH, -OCH-COH, -SOM, ^ N 1O –OSOM', -POM, —OPOM, or mixtures R4 R4 thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y indepen 2. N-s-y-R dently has the value from 0 to 6, each Z independently has the value from 0 to 100; -X -X. 15 i) Substituted aryl, unsubstituted aryl, or mixtures thereof; or the formula: j) Substituted alkylenearyl, unsubstituted alkylenearyl, or R6 mixtures thereof; y sey, k) Substituted aryloxy, unsubstituted aryloxy, or mixtures R4 r thereof; 1) Substituted oxyalkylene aryl, unsubstituted y oxyalkylenearyl, or mixtures thereof; S. m) Substituted alkylene oxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof; 25 n) C-C thioalkyl, C-C branched thioalkyl, or mix / N N \ tures thereof; N III MsR N o) an ester of the formula -COR wherein R is i) C-C alkyl, C-C branched alkyl, C-Cs. R alkenyl, C-C branched alkenyl, or mixtures thereof; Exe N1s * ii) halogen Substituted C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; iii) polyhydroxyl Substituted C-C alkylene; AleXS. SS 35 iv) C-C glycol, x V) C-C alkoxy; Vi) C-C branched alkoxy; vii) Substituted aryl, unsubstituted aryl, or mixtures thereof; wherein M is a photoactive metal or non-metal, Said metal 40 viii) substituted alkyle neary 1, unsubstituted or non-metal Selected from the group consisting of Sn, Pt, alkylenearyl, or mixtures thereof; Pd, Pb and mixtures thereof; R', R,R,R,R, and Runits ix) Substituted aryloxy, unsubstituted aryloxy, or mix are each independently Selected from the group consisting tures thereof; of: X) Substituted oxyalkylene aryl, unsubstituted 45 oxyalkylenearyl, or mixtures thereof; Xi) Substituted alkylene oxyaryl, unsubstituted a) hydrogen; alkyleneoxyaryl, or mixtures thereof; b) halogen; p) an alkyleneamino unit of the formula: c) hydroxy, 50 d) C-C alkyl, C-C branched alkyl, C-C alkenyl, R10 C-C branched alkenyl, or mixtures thereof; - (A):-(CH2) N-R12 X e) halogen Substituted C-C alkyl, C-C branched R11 alkyl C-C alkenyl, C-C branched alkenyl, or 55 mixtures thereof; wherein R'' and R'' are C-C alkyl, C-C- f) polyhydroxyl Substituted C-C alkyl, branched alkyl, C-C alkenyl, C-C branched g) C-C22 alkoxy; alkenyl, or mixtures thereof; R' is: 60 i) hydrogen; h) branched alkoxy having the formula: ii) C-C alkyl, C-C branched alkyl, C-C, alkenyl, C-C branched alkenyl, or mixtures thereof; -O-CH O A is nitrogen or oxygen; X is chlorine, bromine, iodine, 65 or other water Soluble anion, V is 0 or 1, u is from 0 to CH-(O)(CH2)(OCH2CH2); Z. 22; q) an amino unit of the formula: US 6,417,150 B2 39 40 e) halogen Substituted C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or wherein R'' and R' are C-C alkyl, C-C, mixtures thereof; branched alkyl, C-C alkenyl, C-C branched 5 f) polyhydroxyl Substituted C-C alkyl, alkenyl, or mixtures thereof; g) C-C2 alkoxy; r) an alkylethyleneoxy unit of the formula: h) branched alkoxy having the formula:

-(A)-(CH),(OCH-CH).Z. 1O -O-CH O wherein Z is: CH-(O)(CH2)(OCH2CH2); Z. i) hydrogen; -O-CH ii) hydroxyl; 15 iii) -COH: iv) -SOM; v) –OSOM"; Vi) C-C alkoxy; Vii) Substituted aryl, unsubstituted aryl, or mixtures wherein Z is hydrogen, hydroxyl, C-Co alkyl, thereof; C-C alkoxy, -COH, -OCH-COH, -SOM, viii) Substituted aryloxy, unsubstituted aryloxy, or mix –OSOM', -POM, —OPOM, or mixtures tures thereof; thereof; M is a water Soluble cation in Sufficient amount ix) alkyleneanino; or mixtures thereof; 25 to Satisfy charge balance, X is 0 or 1, each y indepen A is nitrogen or oxygen, M is a water Soluble cation, V dently has the value from 0 to 6, each Z independently is 0 or 1, X is from 0 to 100, y is from 0 to 12; has the value from 0 to 100; s) substituted siloxy of the formula: i) Substituted aryl, unsubstituted aryl, or mixtures thereof; OSiR19R20R21 j) Substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; wherein each R', R', and R is independently k) Substituted aryloxy, unsubstituted aryloxy, or mixtures i) C-C alkyl, C-C branched alkyl, C-C2 thereof; alkenyl, C-C branched alkenyl, or mixtures 35 1) Substituted oxyalkylene aryl, unsubstituted thereof; oxyalkylenearyl, or mixtures thereof, ii) Substituted aryl, unsubstituted aryl, or mixtures thereof; m) Substituted alkylene oxyaryl, unsubstituted iii) Substituted aryloxy, unsubstituted aryloxy, or mix alkyleneoxyaryl, or mixtures thereof; tures thereof; 40 n) C-C thioalkyl, C-C branched thioalkyl, or mix iv) an alkylethyleneoxy unit of the formula: tures thereof; o) a carboxylate of the formula:

O wherein Z is: 45 a) hydrogen; b) hydroxyl; c) -COH; d) -SOM; wherein R is: e) —OSOM"; 50 i) C-C alkyl, C-C branched alkyl, C-C2 f) C-C alkoxy; alkenyl, C-C branched alkenyl, or mixtures g) Substituted aryl, unsubstituted aryl, or mixtures thereof; thereof; ii) halogen Substituted C-C alkyl, C-C branched h) Substituted aryloxy, unsubstituted aryloxy, or mix alkyl, C-C alkenyl, C-C branched alkenyl, or tures thereof; 55 i) alkyleneamino; or mixtures thereof; mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, iii) polyhydroxyl Substituted C-C alkylene; v is 0 or 1, X is from 0 to 100, y is from 0 to 12; iv) C-C glycol, V) C-C alkoxy; and mixtures thereof axial R units wherein each R is 60 independently Selected from the group consisting of Vi) C-C branched alkoxy; vii) Substituted aryl, unsubstituted aryl, or mixtures a) hydrogen; thereof; b) halogen; viii) substituted alkyle neary 1, unsubstituted c) hydroxy, 65 alkylenearyl, or mixtures thereof; d) C-C alkyl, C-C branched alkyl, C-C alkenyl, ix) Substituted aryloxy, unsubstituted aryloxy, or mix C-C branched alkenyl, or mixtures thereof; tures thereof; US 6,417,150 B2 41 42 X) Substituted oxyalkylene aryl, unsubstituted b) hydroxyl; oxyalkylenearyl, or mixtures thereof; c) -COH; Xi) Substituted alkylene oxyaryl, unsubstituted d) -SOM"; alkyleneoxyaryl, or mixtures thereof; . 5 e) —OSOM t; p) an alkyleneamino unit of the formula: f) C-C alkoxy; g) Substituted aryl, unsubstituted aryl, or mixtures R10 thereof; h) Substituted aryloxy, unsubstituted aryloxy, or mix -(A)-(CH3)-N'-R12 X- 1O tures thereof; R11 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, y is from 0 to 12; wherein R'' and R'' are C-C alkyl, C-C 15 and mixtures thereof. branched alkyl, C-C alkenyl, C-C branched 2. A method for cleaning a hard Surface comprising alkenyl, or mixtures thereof; R' is: contacting a hard Surface in need of cleaning with an i) hydrogen; ii) C-C alkyl, C-C branched alkyl, C-C2 aqueous cleaning composition comprising at least 0.001 alkenyl, C-C branched alkenyl, or mixtures 20 ppm photoSensitizing compound according to claim 1 and thereof; exposing the hard Surface to a Source of light having a A is nitrogen or oxygen; X is chlorine, bromine, iodine, minimal wavelength range from about 300 to about 1200 or other water Soluble anion, V is 0 or 1, u is from 0 to nanometerS. 22; 25 3. A method for cleaning a stained fabric with a cleaning q) an amino unit of the formula: material comprising a low aqueous cleaning composition -NR7R18 comprising contacting a Stained fabric in need of Stain removal with a low aqueous cleaning Solution comprising wherein R'' and R' are C-C alkyl, C-C, less than 50% water and at least 0.001 ppm of the photo branched alkyl, C-C alkenyl, C-C branched Sensitizing compound according to claim 1 followed by alkenyl, or mixtures thereof; exposing the Surface of the treated fabric to a Source of light r) an alkylethyleneoxy unit of the formula: having a minimal wavelength range from about 300 to about -(A)-(CH2)(OCH2CH2), Z. 35 1200 nanometers. 4. A method for cleaning a hard Surface with a low wherein Z is: i) hydrogen; aqueous cleaning composition comprising contacting a hard ii) hydroxyl; Surface in need of cleaning with a low aqueous cleaning iii) -COH: composition comprising less than 50% water and at least iv) -SOM; 40 0.001 ppm of the photosensitizing compound according to v) —OSOMM"; claimlaim 1 and exposing the hard SurfaceSurf to a Source offligh light Vi) C-C alkoxy; Vii) Substituted aryl, unsubstituted aryl, or mixtures having a minimal wavelength range from about 300 to about thereof; 1200 nanometers. viii) Substituted aryloxy, unsubstituted aryloxy, or mix- 5. A bleaching composition comprising: tures thereof; a) at least about 0.01% of a non-hypohalite bleach; ix) alkyleneamino; or mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, V b) at least about 0.001 ppm of a photosensitizing com is 0 or 1, X is from 0 to 100, y is from 0 to 12; pound having a Q-band maximum absorption wave s) substituted siloxy of the formula: 50 length of 660 nanometers or greater according to claim 1; and OSiR19R20R21 c) the balance carriers and adjunct ingredients. 6. A composition according to claim 5 wherein the non wherein each R', R', and R is independently 55 p 9. i) C-C alkyl, C-C branched alkyl, C-C2 hypohalite bleach is a Selected from the group consisting of alkenyl, C-C branched alkenyl, or mixtures percarboxylic acids, peroxides, percarbonates, perborates, thereof; and mixtures thereof. ii),substituted aryl, unsubstituted aryl, or mixtures 7. A laundry or cleaning composition comprising: CCO iii) Substituteds aryloxy, unsubstituted aryloxy, or mix- 60 A) from about 0.1% by weight, of a detersive Surfactant, tures thereof; Said detersive Surfactant is Selected from the group iv) an alkylethyleneoxy unit of the formula: consisting of anionic, cationic, nonionic, Zwitterionic, ampholytic Surfactants, and mixtures thereof; -(A)-(CH2)(OCH2CH2), Z. 65 B) from about 0.001 ppm of a photosensitizing compound wherein Z is: having a Q-band maximum absorption wavelength of a) hydrogen; 660 nanometers or greater having the formula: US 6,417,150 B2 43 44 -continued 1. R22. -O-CH R y CH-(O)(CH2)(OCH2CH2); Z. R - St. wherein Z is hydrogen, hydroxyl, C-C alkyl, N / N4. \ / N C-C alkoxy, -COH, -OCH-COH, -SO N N 1O M", OSOM', -POM, –OPOM, or mix tures thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y ean-s, independently has the value from 0 to 6, each Z R.-- --R independently has the value from 0 to 100; S-x 15 i) Substituted aryl, unsubstituted aryl, or mixtures thereof; j) Substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; or having the formula: k) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; 1) Substituted oxyalkylene aryl, unsubstituted Xy oxyalkylenearyl, or mixtures thereof; R- as m) Substituted alkylencoxyaryl, unsubstituted / alkyleneoxyaryl, or mixtures thereof; R3 21 % N x3 n) C-C thioalkyl, C-C branched thioalkyl, or 25 mixtures thereof; o) an ester of the formula -COR wherein R is R P. i) C-C alkyl, C-C branched alkyl, C-C y N N \ alkenyl, C-C branched alkenyl, or mixtures N Rii III.M-sR N thereof; / N ii) halogen Substituted C-C alkyl, C-C, N N branched alkyl, C-C alkenyl, C-C branched R2 R2 alkenyl, or mixtures thereof; 2a s N / iii) polyhydroxyl Substituted C-C alkylene; iv) C-C22 glycol, 35 V) C-C alkoxy; SXR1 R1s i. Vi) C-C branched alkoxy; na SAS1 Vii) Substituted aryl, unsubstituted aryl, or mixtures R6 R6 thereof; viii) substituted alkylene aryl, unsubstituted 40 alkylenearyl, or mixtures thereof; wherein M is a photoactive metal or non-metal, Said ix) Substituted aryloxy, unsubstituted aryloxy, or metal or non-metal Selected from the group consisting mixtures thereof; X) Substituted oxyalkylene aryl, unsubstituted of Sn, Pt, Pd, P and mixtures thereof; R', R. R. R", oxyalkylenearyl, or mixtures thereof; R, and R units are each independently selected from 45 Xi) Substituted alkyleneoxyaryl, unsubstituted the group consisting of: alkyleneoxyaryl, or mixtures thereof; a) hydrogen; p) an alkyleneamino unit of the formula: b) halogen; c) hydroxy, 50 R10 d) C-C alkyl, C-C branched alkyl, C-C2 - (A) -(CH2) N-R12 X alkenyl, C-C branched alkenyl, or mixtures thereof; R11 e) halogen Substituted C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or 55 wherein R'' and R' are C-C alkyl, C-C, branched alkyl, C-C alkenyl, C-C branched mixtures thereof; alkenyl, or mixtures thereof; R' is: f) polyhydroxyl Substituted C-C alkyl, i) hydrogen; g) C-C2 alkoxy; ii) C-C alkyl, C-C branched alkyl, C-C h) branched alkoxy having the formula: 60 alkenyl, C-C branched alkenyl, or mixtures thereof; CH-(O).(CH2)(OCH2CH3); Z. A is nitrogen or oxygen; X is chlorine, bromine, iodine, or other water Soluble anion, V is 0 or 1, u is -O-CH O from 0 to 22; 65 CH-(O).(CH2)(OCH2CH3); Z. q) an amino unit of the formula: US 6,417,150 B2 45 46 wherein R'' and R' are C-C alkyl, C-C, h) branched alkoxy having the formula: branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; CH-(O)(CH2)(OCH2CH3); Z. r) an alkylethyleneoxy unit of the formula: -O-CH O -(A)-(CH2)(OCH2CH2), Z. CH-(O)(CH2)(OCH2CH2); Z. wherein Z is: -O-CH i) hydrogen; ii) hydroxyl; 1O iii) -COH: iv) -SOM"; v) –OSOM t; Vi) C-C alkoxy; wherein Z is hydrogen, hydroxyl, C-Co alkyl, Vii) Substituted aryl, unsubstituted aryl, or mixtures 15 C-C alkoxy, -COH, -OCH-COH, -SOM, thereof; –OSOM", POM, –OPOM, or mixtures viii) Substituted aryloxy, unsubstituted aryloxy, or thereof; M is a water Soluble cation in Sufficient amount mixtures thereof; to Satisfy charge balance, X is 0 or 1, each y indepen ix) alkyleneamino; or mixtures thereof; dently has the value from 0 to 6, each Z independently A is nitrogen or oxygen, M is a water Soluble cation, has the value from 0 to 100; v is 0 or 1, X is from 0, to 100, y is from 0 to 12; s) substituted siloxy of the formula: i) Substituted aryl, unsubstituted aryl, or mixtures thereof; j) Substituted alkylenearyl, unsubstituted alkylenearyl, or OSiR19R20R21 25 mixtures thereof; wherein each R', R', and R is independently k) Substituted aryloxy, unsubstituted aryloxy, or mixtures i) C-C alkyl, C-C branched alkyl, C-C thereof; alkenyl, C-C branched alkenyl, or mixtures 1) Substituted oxyalkylene aryl, unsubstituted thereof; oxyalkylenearyl, or mixtures thereof; ii) Substituted aryl, unsubstituted aryl, or mixtures thereof; m) Substituted alkylene oxyaryl, unsubstituted iii) Substituted aryloxy, unsubstituted aryloxy, or alkyleneoxyaryl, or mixtures thereof; mixtures thereof; n) C-C thioalkyl, C-C branched thioalkyl, or mix iv) an alkylethyleneoxy unit of the formula: 35 tures thereof; -(A)-(CH),(OCH-CH).Z. o) a carboxylate of the formula: wherein Z is: O a) hydrogen; 40 b) hydroxyl; c) -COH; d) -SOM; wherein R is: e) —OSOM"; f) C-C alkoxy; 45 i) C-C alkyl, C-C branched alkyl, C-C, g) Substituted aryl, unsubstituted aryl, or mixtures alkenyl, C-C branched alkenyl, or mixtures thereof; thereof; h) Substituted aryloxy, unsubstituted aryloxy, or ii) halogen Substituted C-C alkyl, C-C branched mixtures thereof; alkyl, C-C alkenyl, C-C branched alkenyl, or i) alkyleneamino; or mixtures thereof; 50 mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, V is 0 or 1, X is from 0 to 100, y is from 0 iii) polyhydroxyl Substituted C-C alkylene; to 12; iv) C-C glycol, and mixtures thereof axial R units wherein each R is V) C-C alkoxy; independently Selected from the group consisting of 55 Vi) C-C branched alkoxy; a) hydrogen; vii) Substituted aryl, unsubstituted aryl, or mixtures b) halogen; thereof; c) hydroxy, viii) substituted alkyle neary 1, unsubstituted d) C-C alkyl, C-C branched alkyl, C-C alkenyl, 60 alkylenearyl, or mixtures thereof; C-C branched alkenyl, or mixtures thereof; ix) Substituted aryloxy, unsubstituted aryloxy, or mix e) halogen Substituted C-C alkyl, C-C branched tures thereof; alkyl, C-C alkenyl, C-C branched alkenyl, or X) Substituted oxyalkylene aryl, unsubstituted mixtures thereof; 65 oxyalkylenearyl, or mixtures thereof; f) polyhydroxyl Substituted C-C alkyl, Xi) Substituted alkylene oxyaryl, unsubstituted g) C-C22 alkoxy; alkyleneoxyaryl, or mixtures thereof; US 6,417,150 B2 47 48 p) an alkyleneamino unit of the formula: h) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; R10 i) alkyleneamino; or mixtures thereof; -(A)-(CH3)-N'-R12 X A is nitrogen or oxygen, M is a water Soluble cation, v is 0 or 1, X is from 0 to 100, y is from 0 to 12; R11 and mixtures thereof, and C) the balance carriers and adjunct ingredients. wherein R'' and R'' are C-C alkyl, C-C, 8. A composition according to claim 7 comprising from branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures thereof; R' is: about 0.01 ppm to about 10000 ppm of said photosensitizing i) hydrogen; compound. ii) C-C alkyl, C-C branched alkyl, C-C2 9. A composition according to claim 8 comprising from alkenyl, C-C branched alkenyl, or mixtures about 0.1 ppm to about 5000 ppm of said photosensitizing thereof; 15 compound. A is nitrogen or oxygen; X is chlorine, bromine, iodine, 10. A composition according to claim 9 comprising from or other water Soluble anion, V is 0 or 1, u is from 0 to about 10 ppm to about 1000 ppm of said photosensitizing 22; compound. q) an amino unit of the formula: 11. A composition according to claim 7 wherein the photosensitizing compound comprises R', R. R. R', R, -NR17R18 and Runits independently selected from the group consist wherein R'' and R' are C-C alkyl, C-C, ing of hydrogen, hydroxyl, halogen, C-C thioalkyl, branched alkyl, C-C alkenyl, C-C branched C-C branched thioalkyl, C-C alkoxy, C-C, alkenyl, or mixtures thereof; 25 branched alkoxy, aryloxy, an alkylethyleneoxy unit of the r) an alkylethyleneoxy unit of the formula: formula: -(A)-(CH),(OCH-CH).Z. -(A)-(CH2)(OCH2CH2), Z. wherein Z is: wherein Z comprises hydrogen, hydroxyl, -COH, -SO i) hydrogen; M', -OSOM", C-C alkoxy, Substituted and unsubsti ii) hydroxyl; tuted aryl, Substituted and unsubstituted aryloxy, alkylene iii) -COH; amino; and mixtures thereof, A comprises nitrogen or iv) -SOM"; oxygen, M is a water Soluble cation, V is 0 or 1, X is from v) –OSOM; 35 Vi) C-C alkoxy; 0 to 100, y is from 0 to 12. Vii) Substituted aryl, unsubstituted aryl, or mixtures 12. A composition according to claim 2 wherein axial R thereof; units comprise: viii) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; a) alkylethyleneoxy units of the formula ix) alkyleneamino; or mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, V -(A)-(CH),(OCH-CH).Z. is 0 or 1, X is from 0 to 100, y is from 0 to 12; s) substituted siloxy of the formula: wherein Z comprises hydrogen, hydroxyl, -CO2H, 45 OSiR1R20R21 -SOM', -OSOM", C-C alkoxy, Substituted and unsubstituted aryl, Substituted and unsubstituted wherein each R', R', and R is independently aryloxy, alkyleneamino; A comprises nitrogen or i) C-C alkyl, C-C branched alkyl, C-C, Oxygen, M is a water Soluble cation, V is 0 or 1, X is alkenyl, C-C branched alkenyl, or mixtures 50 from 0 to 100, y is from 0 to 12; thereof; b) branched alkoxy having the formula ii) Substituted aryl, unsubstituted aryl, or mixtures thereof; iii) Substituted aryloxy, unsubstituted aryloxy, or mix CH-(O)(CH2)(OCH2CH2); B tures thereof; 55 -O-CH O iv) an alkylethyleneoxy unit of the formula: CH-(O)(CH2)(OCH2CH2); B -(A)-(CH),(OCH-CH).Z. -O-CH wherein Z is: CH- (O)(CH2)(OCH2CH2): B a) hydrogen; 60 b) hydroxyl; c) -COH; d) -SOM"; e) —OSOM t; wherein B is hydrogen, hydroxyl, C-C alkyl, f) C-C alkoxy; 65 C-C alkoxy, -COH, -CHCOH, -SOM, g) Substituted aryl, unsubstituted aryl, or mixtures –OSOM', -POM, —OPOM, and mixtures thereof; thereof; M is a water Soluble cation in Sufficient amount US 6,417,150 B2 49 SO to Satisfy charge balance, X is 0 or 1, each y indepen dently has the value from 0 to 6, each Z independently R1 has the value from 0 to 100; c) substituted siloxy of the formula A ra -OSiR7RR wherein each R', R, and R is independently selected y—NN from the group consisting of C-C alkyl, C-C, N Rii II M-sR N branched alkyl, C-C alkenyl, C-C branched 1O ^ N alkenyl, Substituted and unsubstituted aryl, Substituted R4 R4 and unsubstituted aryloxy, an alkylethyleneoxy unit of 2. N-s-y-R the formula 15 y-x. -x. -(A)-(CH2)(OCH2CH2), Z. or having the formula:

wherein Z comprises hydrogen, C-C alkyl, R 5 hydroxyl, -COH, -SOM', -OSOM", C-C, an alkoxy, Substituted and unsubstituted aryl, Substituted 7. R4 and unsubstituted aryloxy, alkyleneamino, and mix x tures thereof, A units comprise nitrogen or oxygen, M ''' S. R3 is a water Soluble cation, V is 0 or 1, X is from 0 to 100, y is from 0 to 12. 25 R2 13. A composition according to claim 12 wherein R is a y/ Nr N1. t\ branched alkoxy having the formula: N Rii II. Mrs.R N / N N N R2 R2 CH-(O).(CH2)(OCH2CH2); B Xa s N A. -O-CH O R4 N Ás CH-(O)(CH2)(OCH2CH2); B R 35 ASS, i. U Sa YleX S1 5 R6 R6A. x wherein M is a photoactive metal or non-metal Selected from the group consisting of Sn, Pt, Pd, P and mixtures 40 thereof; R", R. R. R. R., and R units are moieties that provide a positive A, yield of at least 1 when said moiety replaces hydrogen; wherein the R units are axial units, said R units wherein B is hydrogen, hydroxyl, C-Co alkyl, C-Co independently Selected from the group consisting of: alkoxy, -COH, -CHCOH, -SOM', -OSOM", 45 a) hydrogen; b) halogen; -POM,-OPOM, and mixtures thereof; M is a water c) hydroxy, Soluble cation in Sufficient amount to Satisfy charge balance; d) C-C alkyl, C-C branched alkyl, C-C, X is 0 or 1, each y independently has the value from 0 to 6, alkenyl, C-C branched alkenyl, or mixtures each Z independently has the value from 0 to 100. 50 thereof; e) halogen Substituted C-C alkyl, C-C branched 14. A composition according to claim 7 wherein the alkyl, C-C alkenyl, C-C branched alkenyl, or adjunct ingredients are members Selected from the group mixtures thereof; f) polyhydroxyl Substituted C-C alkyl, consisting of buffers, builders, chelants, filler Salts, Soil g) C-C alkoxy; release agents dispersants, enzymes, enzyme boosters, 55 h) branched alkoxy having the formula: perfumes, thickeners, Solvents, clayS, bleaches, and mixtures thereof. ti- (O).(CH2)(OCH2CH3); Z. 15. A laundry or cleaning composition comprising: -O-CH O A) from about 0.1% by weight, of a detersive surfactant, 60 Said detersive Surfactant is Selected from the group CH-(O)(CH2)(OCH2CH2); -Z consisting of anionic, cationic, nonionic, Zwitterionic, -O-CH ampholytic Surfactants, and mixtures thereof; QH-(O)(CH3),(OCH2CH3); -Z B) from about 0.001 ppm of a photosensitizing compound 65 having a Q-band maximum absorption wavelength of 660 nanometers or greater having the formula: US 6,417,150 B2 S1 52 wherein Z is hydrogen, hydroxyl, C-Co alkyl, r) an alkylethyleneoxy unit of the formula: C-C alkoxy, -COH, OCHCO, -SO M',-- -OSOM',-R -- -POM,2 –OPOM, or mix tures thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y wherein Z is: independently has the value from 0 to 6, each Z independently has the value from 0 to 100; i) hydrogen; i) Substituted aryl, unsubstituted aryl, or mixtures ii) hydroxyl; thereof; iii) -COH: j) Substituted alkylenearyl, unsubstituted alkylenearyl, iv) -SOM"; or mixtures thereof; 1O v) –OSOM t; k) Substituted aryloxy, unsubstituted aryloxy, or mix Vi) C-C alkoxy; tures thereof; Vii) Substituted aryl, unsubstituted aryl, or mixtures 1) Substituted oxyalkylene aryl, unsubstituted thereof; oxyalkylenearyl, or mixtures thereof; viii) Substituted aryloxy, unsubstituted aryloxy, or m) Substituted alkylene oxyaryl, unsubstituted 15 alkyleneoxyaryl, or mixtures thereof; mixtures thereof; n) C-C thioalkyl, C-C branched thioalkyl, or ix) alkyleneamino; or mixtures thereof; mixtures thereof; A is nitrogen or oxygen, M is a water Soluble cation, o) a carboxylate of the formula: v is 0 or 1, X is from 0 to 100, y is from 0 to 12; s) substituted siloxy of the formula: O OSiR19R20R21 -O-C-R wherein each R', R', and R is independently wherein R is: 25 i) C-C alkyl, C-C branched alkyl, C-C i) C-C alkyl, C-C branched alkyl, C-C alkenyl, C-C branched alkenyl, or mixtures alkenyl, C-C branched alkenyl, or mixtures thereof; thereof; ii) Substituted aryl, unsubstituted aryl, or mixtures ii) halogen Substituted C-C alkyl, C-C thereof; branched alkyl, C-C alkenyl, C-C branched iii) Substituted aryloxy, unsubstituted aryloxy, or alkenyl, or mixtures thereof; iii) polyhydroxyl Substituted C-C alkylene; mixtures thereof; iv) C-C glycol, iv) an alkylethyleneoxy unit of the formula: v) C-C alkoxy; Vi) C-C branched alkoxy; -(A)-(CH),(OCH-CH).Z. Vii) Substituted aryl, unsubstituted aryl, or mixtures 35 thereof; wherein Z is: viii) substituted alkylene aryl, unsubstituted a) hydrogen; alkylenearyl, or mixtures thereof; b) hydroxyl; ix) Substituted aryloxy, unsubstituted aryloxy, or c) -COH; mixtures thereof; 40 d) -SOM"; X) Substituted oxyalkylene aryl, unsubstituted e) —OSOM"; oxyalkylenearyl, or mixtures thereof; f) C-C alkoxy; Xi) Substituted alkyleneoxyaryl, unsubstituted g) Substituted aryl, unsubstituted aryl, or mixtures alkyleneoxyaryl, or mixtures thereof; thereof; p) an alkyleneamino unit of the formula: 45 h) Substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; R10 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, y is from 0 R11 50 to 12; and mixtures thereof, and wherein R'' and R'' are C-C alkyl, C-C, B) the balance carriers and adjunct ingredients. branched alkyl, C-C alkenyl, C-C branched 16. A composition according to claim 15 wherein Said alkenyl, or mixtures thereof; R' is: 55 photosensitizing compound has a positive A,i, yield of at i) hydrogen; least 10. ii) C-C alkyl, C-C branched alkyl, C-C, 17. A composition according to claim 16 wherein Said alkenyl, C-C branched alkenyl, or mixtures photosensitizing compound has a positive A,i, yield of at thereof; least 30. A is nitrogen or oxygen; X is chlorine, bromine, 18. A laundry or cleaning composition comprising: iodine, or other water Soluble anion, V is 0 or 1, u is 60 from 0 to 22; A) from about 0.1% by weight, of a detersive surfactant, q) an amino unit of the formula: Said detersive Surfactant is Selected from the group consisting of anionic, cationic, nonionic, Zwitterionic, -NR17R18 ampholytic Surfactants, and mixtures thereof; wherein R7 and R' are C-C alkyl, C-C, 65 B) from about 0.001 ppm of a photosensitizing compound branched alkyl, C-C alkenyl, C-C branched having a Q-band maximum absorption wavelength of alkenyl, or mixtures thereof; 660 nanometers or greater having the formula: US 6,417,150 B2 S3 S4 h) branched alkoxy having the formula: CH-(O)(CH2)(OCH2CH3); Z.

-O-CH O CH-(O)(CH2)(OCH2CH2); Z. / N.4 \ -O-CH CHH (O).(CH2)(OCH2CH3); Z. =Y N 1O

wherein Z is hydrogen, hydroxyl, C-C alkyl, te Cl4.ye." 15 C-C alkoxy, -COH, -OCH-COH, -SO M', -OSOM', -POM, –OPOM, or mix tures thereof; M is a water Soluble cation in Sufficient amount to Satisfy charge balance, X is 0 or 1, each y or having the formula: 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, 25 or mixtures thereof; k) Substituted aryloxy, unsubstituted aryloxy, or mix tures thereof; 1) Substituted oxyalkylene aryl, unsubstituted oxyalkylenearyl, or mixtures thereof; m) Substituted alkylene oxyaryl, unsubstituted "y s alkyleneoxyaryl, or mixtures thereof; N N R2 R2 n) C-C thioalkyl, C-C branched thioalkyl, or Xa s S A. 35 mixtures thereof; R4 R3 o) a carboxylate of the formula: S SAS R3 S. R1 A.-R. O 40

wherein R is: i) C-C alkyl, C-C branched alkyl, C-C, wherein M is a photoactive metal or non-metal Selected 45 alkenyl, C-C branched alkenyl, or mixtures from the group consisting of Sn, Pt, Pd, Pb, and thereof; mixtures thereof; ii) halogen Substituted C-C alkyl, C-C2 R", R. R. R. R., and R units are moieties that branched alkyl, C-C alkenyl, C-C branched provide a positive red shift value of at least 1 when said 50 alkenyl, or mixtures thereof; moieties are Substituted for hydrogen; iii) polyhydroxyl Substituted C-C alkylene; R units are axial units, Said R units independently iv) C-C22 glycol, Selected from the group consisting of: V) C-C alkoxy; a) hydrogen; 55 Vi) C-C branched alkoxy; b) halogen; Vii) Substituted aryl, unsubstituted aryl, or mixtures c) hydroxy, thereof; d) C-C alkyl, C-C branched alkyl, C-C2 viii) substituted alkylene aryl, unsubstituted alkenyl, C-C branched alkenyl, or mixtures 60 alkylenearyl, or mixtures thereof; thereof; ix) Substituted aryloxy, unsubstituted aryloxy, or e) halogen Substituted C-C alkyl, C-C branched mixtures thereof; alkyl, C-C alkenyl, C-C branched alkenyl, or X) Substituted oxyalkylene aryl, unsubstituted mixtures thereof; 65 oxyalkylenearyl, or mixtures thereof; f) polyhydroxyl Substituted C-C alkyl, Xi) Substituted alkyleneoxyaryl, unsubstituted g) C-C alkoxy; alkyleneoxyaryl, or mixtures thereof; US 6,417,150 B2 SS S6 p) an alkyleneamino unit of the formula: s) substituted siloxy of the formula:

R10 OSiR1R20R21 -(A)-(CH3)-N'-R12 X wherein each R', R', and R is independently i) C-C alkyl, C-C branched alkyl, C-C, R11 alkenyl, C-C branched alkenyl, or mixtures thereof; wherein R'' and R'' are C-C alkyl, C-C, ii) Substituted aryl, unsubstituted aryl, or mixtures branched alkyl, C-C alkenyl, C-C branched 1O thereof; alkenyl, or mixtures thereof; R' is: iii) Substituted aryloxy, unsubstituted aryloxy, or i) hydrogen; mixtures thereof; ii) C-C alkyl, C-C branched alkyl, C-C, iv) an alkylethyleneoxy unit of the formula: alkenyl, C-C branched alkenyl, or mixtures thereof; -(A)-(CH),(OCH-CH).Z. A is nitrogen or oxygen; X is chlorine, bromine, 15 iodine, or other water Soluble anion, V is 0 or 1, u is wherein Z is: from 0 to 22; a) hydrogen; q) an amino unit of the formula: b) hydroxyl; c) -COH; -NR17R18 d) -SOM"; wherein R7 and R' are C-C alkyl, C-C, e) —OSOM t; branched alkyl, C-C alkenyl C-C branched f) C-C alkoxy; alkenyl, or mixtures thereof; g) Substituted aryl, unsubstituted aryl, or mixtures r) an alkylethyleneoxy unit of the formula: thereof; 25 h) Substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; wherein Z is: i) alkyleneamino; or mixtures thereof; i) hydrogen; A is nitrogen or oxygen, M is a water Soluble ii) hydroxyl; cation, V is 0 or 1, X is from 0 to 100, y is from 0 iii) -COH: to 12; iv) -SOM; and mixtures thereof, and v) –OSOM; B) the balance carriers and adjunct ingredients. Vi) C-C alkoxy; 19. A composition according to claim 18 wherein said Vii) Substituted aryl, unsubstituted aryl, or mixtures is photosensitizing compound has a positive red shift of at least thereof; viii) Substituted aryloxy, unsubstituted aryloxy, or 20. A composition according to claim 19 wherein said mixtures thereof; photosensitizing compound has a positive red shift of at least 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, y is from 0 to 12;