AU3094899A - A composition comprising a photo-oxidising agent and uses of the agent - Google Patents

Description

WO 00/52101 PCT/US99/05795 A COMPOSITION COMPRISING A PHOTO-OXIDISING AGENT AND USES OF THE AGENT 5 Technical Field 10 The present invention relates to the use of specific photo-oxidation agents in photo oxidation methods which require a high surface activity and solubility of the photo oxidising agent. The invention also provides photo-oxidation compositions. 15 Background to the Invention Various compounds are known in the art which, upon exposure to light, can be photo activated, to become an active species for chemical or further photo-chemical reactions. These materials can be used for a number of applications, including bleaching and 20 disinfecting, such as for example described in W097/05203. Two general examples of these type of compounds are porphyrin and phthalocyanine photo-bleaching compounds. These compounds, unmetallated and especially when combined with a suitable cation, can undergo a series of reactions, starting with a 25 photochemical reaction step which transforms the compound into an excited state. The excited state of the molecule can aid oxidation reactions or alternatively, after subsequent reaction steps in conjunction with molecular oxygen, it can produce "active oxygen". Active oxygen includes molecules of "singlet oxygen" or superoxide. Superoxide can subsequently be converted to hydrogen peroxide. "Singlet oxygen" , superoxide or 30 hydrogen peroxide, formed in this series of reactions, are also oxidative species. Examples of porphyrins or porphyrin-like compounds include haematoporphyrin, chlorophyll, WO 00/52101 PCTIUS99/05795 2 chlorin, oxo-chlorins, pheophorbide, pyropheophorbide, benzoporphyrins, tetra arylporphyrin, zinc tetraphenylporphyrin, tripyrroledimethane-derived expanded porphyrins. Examples of phthalocyanines and naphthalocyanines include zinc, aluminum, indium, silicon, and gallium phthalocyanines and naphthalocyanines, the most common 5 being the zinc and aluminium phthalocyanines. Other examples of photobleaches are xanthene dyes such as rose bengal, eosin, and fluorescein. Additional photobleach examples include metachromic dyes such as thionine, methylene blue, benzo[a]phenoxazinium (Nile Blue A), and benzo[a]phenothiazinium. A 1o limitation to the use of some of these more water-soluble photo-bleaches can be their poor surface-activity. One problem associated with the use of phthalocyanine, naphthalocyanines, and porphyrin photo-bleaching compounds arises from the fact that these are not water soluble, in is particular when the parent rings are substituted solely with hydrogen. In an effort to do make these compounds more water-soluble, for example phthalocyanine derivatives have been modified with various solubilising substituents, for example described in EP-1 19746, EP-379312, EP-553608, EP-596187 and EP-692947. These documents teach selected substituent units that are hydrophilic and which are bonded to the photo-sensitive ring 20 units to enhance the solubility or photochemical properties of the molecule. In general, three or more substituents are needed to obtain the required solubility. A problem relating to the introduction of (high numbers of) substituent groups to the photo-bleaching compound (to ensure a certain level of water solubility) is that the photo 25 bleaching properties of the ring system are often affected. For example, a change which increases solubility may reduce the quantum efficiency of the molecule. Firstly, this can lead to less formation of singlet. Secondly, the absorption spectrum may change, leading to an undesirable colouring of the oxidising compounds in use. Also, the preparation of these substituted compounds can proceed in low yield which introduces impurities and increases 30 cost. These impurities may also introduce undesirable colouring. Yet another limitation of most of these substituted compounds is that introduction of solubilising substituent groups WO 00/52101 PCT/US99/05795 3 tends to destabilise the compounds so that they tend to decompose once exposed to light, in particular sunlight, which deactivates them thus leading to a lesser performance. Another major limitation to the use of most of the above compounds known is that they 5 are highly coloured materials (having an absorption in the range of 600-800 nanometres), and thus high concentrations of these compounds will thus lead to staining. Thereto, co-pending application GB 9719779.2 provides improved photo-bleaching agents with the desired absorption spectrum, which are water-soluble and which have an 10 improved surface-activity, comprising water-insoluble or slightly water-soluble photo bleaching compounds integrated or mixed with a specific polymeric compound. More specific and effective bleaching is hereby achieved. Furthermore, they have found that these photo-bleaching agent migrates more evenly to the fabric surface. The inventors of the present invention also found another class of photo-bleaching agents, described herein 15 as agent II, to provide an improved photo-bleaching performance Also, a more efficient photo-bleaching may be achieved under certain conditions, in particular when another bleaching agent is present, because these agents can be more stable when exposed to reagents such as bleach (when present). 20 It has now been found that these new agents can also provide improved oxidation or bleaching under influence of light in various other applications where a good surface activity and also a good water-solubility is required. These applications can benefit form the more efficient and/ or effective oxidation or bleaching provided by these new agents. 25 Furthermore, it has been found that these new agent have a higher light absorption, resulting in an improved performance. Also, a more efficient or effective oxidation or bleaching is achieved, because they tend to be more stable than the prior art agents. It has been found that, due to their improved surface activity and water solubility, the new 30 oxidising agents are for example very useful for bleaching of pulp, paper or yarn. Also, they are useful in hair-bleaching.

WO 00/52101 PCT/US99/05795 4 Also, they have been found to be very effective disinfecting agents or bactericidal, fungicidal, algicidal or herbicidal agents, because of their improved light absorption, improved solubility and surface activity. They are also useful for water purification, not 5 only to kill micro-organisms, but also to react with organic pollutants present in the water. Furthermore, the agents can be useful in photo-dynamic therapy. All documents cited in the present description are, in relevant part, incorporated herein by reference. 10 Summary of the Invention The invention relates to the use of a photo-oxidising agent (I) or (II) or mixtures thereof and compositions comprising these photo-oxidising agent (I) and/ or (II): 15 - photo-oxidising agent ( I) being a polymeric component and a photo-oxidising component, integrated with one another, whereby the weight ratio of the polymeric component to the photo-oxidising component is from 1:1 to 1000:1; - photo-oxidising agent (II) being a mixture of a water-soluble polymer and a photo 20 oxidising component being a mixture of non-charged hydrophobic photo-oxidising compounds and nonbonded ligand selected from the group consisting of compounds capable of binding axially to a Si, Al, Ga, Ge or Sn phthalocyanine moiety and said photo oxidising compounds are selected from the group consisting of Si, Al, Ga, Ge and Sn phthalocyanines having a bonded ligand in at least one axial position and having solid form 25 at ambient temperature in the absence of impurities. Detailed Description of the Invention Photo-oxidising Agent (I) 30 The first group of photo-oxidising agents useful herein are described in co-pending application GB9719779.2. These photo-oxidising agent (I) comprises one or more WO 00/52101 PCTIUS99/05795 5 specific polymeric components and one or more photo-oxidising components integrated with one another, as described herein. 'Integrated with one another' when used herein refers to the integration between the 5 components of the agent, which is obtainable by a process comprising the steps of a) forming a melt of or a solution, comprising a photo-oxidising compound and a polymeric compound; 10 b) in a further step, forming and separating the photo-oxidising agent. This may mean that the photo-oxidising component is adsorbed onto or absorbed in the polymeric component, or that the polymeric component and the photo-oxidising component form an associative complex-structure or coacervate complex-structure. 15 The weight ratio of the polymeric component to the photo-oxidising component in the photo-oxidising agent (I) is from 1:1 to 1000:1, more preferably from 5:1 to 1000:1, more preferably 20:1 to 100:1, most preferably from 20:1 to 60:1 20 The photo-oxidising agent (I) of the invention preferably comprises from 50% to 99.9% by weight, more preferably from 90% to 99.9% by weight, more preferably from 92% to 99% by weight, most preferably from 95% to 98% by weight the polymeric component. The photo-oxidising agent (I) preferably comprises from 0.1% to 50 % by weight, more 25 preferably from 0.1% to 10% by weight, more preferably from 1% to 8% by weight most preferably from 2% to 5% by weight the photo-oxidising component. The precise level will depend on the application. The polymeric compounds for integration with a photo-oxidising compound to form the 30 polymeric component of the photo-oxidising agent (I) of the invention, preferably comprises polymerised monomeric units which comprise di-polar, aprotic groups.

WO 00/52101 PCT/US99/05795 6 Preferably, at least 50%, more preferably at least 75%, more preferably at least 90%, even more preferably at least 95% of the polymerised monomeric units comprise a di-polar, aprotic group. The polymeric compounds can be homo-polymers, comprising a backbone having one type of polymerised monomeric units, or co-polymers comprising a backbone 5 having different polymerised monomeric units. The polymeric compounds preferably have a number average molecular weight of from 500 to 1,000,000, more preferably from 1,000 to 100,000, more preferably from 2000 to 80,000, most preferably from 5000 to 60,000. 10 Highly preferred for photo-oxidising agent (I) are vinylamides such as N-vinylpyrrolidone and N-vinylacetamide as well as vinylheterocycles such as N-vinylimidazole, N vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine-N-oxide. These dipolar, aprotic group-containing monomeric units are particularly effective for solubilising the photo-oxidising component. 15 Co-monomers can be used for photo-oxidising agent (I) to confer additional properties to the polymer such as charge, hydrophilicity and hydrophobicity. Suitable comonomers include acrylic acid or methacrylic acid, their salts, and their esters including methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, ethylhexyl, decyl, lauryl, i-bornyl, cetyl, 20 palmityl, phenoxyethyl, stearylacrylate. Also included are diethylaminoethylacrylate, dimethylaminoethylacrylate, dimethylaminopropylacrylate, and choline esters of acrylic or methacrylic acid. Also included are acrylamide or methacrylamide and their various N substituted derivatives including N-methylol-acrylamide, N,N dimethylaminopropylacrylamide, N,N,N-trimethylammoniumpropylacrylamide, N,N 25 diethylaminopropylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N undecylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid. Also included are vinyl esters such as vinyl acetate, vinyl propionate, vinyllaurate, neooctanoic acid vinylester, neononanoic acid vinylester, neodecanoic acid vinylester. Also included are other vinyl monomers such as styrene, vinyltoluene, c-methylstyrene. Also included are unsaturated 30 acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or their respective anhydride or esters.

WO 00/52101 PCTIUS99/05795 7 Most preferred polymeric compounds for photo-oxidising agent (I) are polyvinylimidazole (PVI), or a copolymer of polyvinylpyrrolidinone and polyvinylimidazole (PVPVI), most preferably polyvinylpyrrolidinone (PVP). Preferably, these highly preferred polymeric 5 compounds have an average molecular weight of from 20,000 to 60,000. Also, mixtures of two or more polymeric compounds can be used for integration with a photo-oxidising compound to form the polymeric component of the photo-oxidising agent (I) herein. 10 The photo-oxidising compound for integration with a polymeric compound to form the photo-oxidising component of the photo-oxidising agent (I) can be any compound known in the art which can undergo a reaction or a series of reactions, starting with a photochemical reaction in conjunction with molecular oxygen to produce molecules of 15 "active oxygen". Active oxygen includes molecules of "singlet oxygen" or superoxide. Superoxide can subsequently be converted to hydrogen peroxide. "Singlet oxygen" , superoxide or hydrogen peroxide, formed in this series of reactions, are oxidative species capable of reacting with stains to chemically bleach them to a colourless and usually water soluble state, thereby resulting in what is called photochemical bleaching. 20 Preferred photo-oxidising compounds are compounds having a porphin or porphyrin structure. Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will 25 include porphyrin. The porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn. 30 WO 00/52101 PCT/US99/05795 8 It can be preferred that the photo-oxidising compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties. 5 The photo-oxidising compound or component can have solubilising groups as substituents, however, for the present invention it is preferred that the photo-oxidising compound or component has only 2 or less solubilising substituent groups. Even more preferably the photo-oxidising compound or component has no solubilising substituent groups, or most 1o preferably is unsubstituted. Highly preferred photo-oxidising compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above. Highly preferred are the phot-oxidising components examplified in example 1 and 2 of co 15 pending application GB9719779.2. Co-pending application GB9719779.2. also described the methods for making the photo oxidising agent (I) as described herein above. 20 Photo-oxidising Agent (II) The polymeric compound of photo-bleaching agent (II) is a water-soluble polymer. The term "water-soluble" used in conjunction with the water-soluble polymers means that these are polymers capable of substantially complete dissolution in water at least one temperature in the range from about 4 'C to about 100 'C. "Substantially" complete means 25 that, at least one temperature in said range, it is possible to put one part by weight of the water-soluble polymer into one hundred parts by weight deionized water, to stir for any suitable period, for example one hour to dissolve the water-soluble polymer, and to filter the resulting solution through a 1 micron filter, to examine the filter, and to find less than 0.1%, preferably less than 0.01% residue on the filter. 30 WO 00/52101 PCT/US99/05795 9 Water-soluble polymers selected for use herein preferably have solubility parameters in the 1/2 1/2 range from about 15 to about 42 MPa 2, preferably 16 to 35 MPa , more preferably 17 to 30 MPa' 12 . The solubility parameter for polyethylene glycol 4,000, an especially useful water-soluble polymer herein, at 25'C is in the range from 18.9 to 22.5 MPal/ 2 . The 5 solubility parameter, also known as the Hildebrand parameter, is as defined in the Physical Properties of Polymers Handbook, Ed. J.E. Mark, AIP Press, 1996; and Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters, A.F.M. Barton, CRC Press, 1990. 10 Water-soluble polymers selected for the photo-oxidising agents (II) are generally solid at room temperature but molten or fluid below about 100*C, more preferably those that are molten or fluid at temperatures in the range from about 4'C to about 95'C, more typically from about 35*C to about 80'C. 15 The water-soluble polymers may optionally include limited proportions of hydrophobic moieties such as relatively short, e.g., C 1

-C

8 , preferably C 1

-C

4 alkyl moieties, optionally in amide, ether or ester side-chains, provided that they remain water-soluble. The water-soluble polymers of photo-bleaching agent (II) can vary in terms of molecular 20 weight provided that they remain water-soluble. The water-soluble polymer can in general have a number average molecular weight that varies widely, e.g., from about 500 to 1,000,000, more preferably from 1,000 to 100,000, more preferably still, from about 1,000 to 10,000. 25 Highly preferred water-soluble polymers will be anhydrous or near-anhydrous at the point at which they are being combined with the photo-oxidising compound. A preferred group of water-soluble polymers are water-soluble polymers which consist essentially of C, H, N and 0, which are liquid or molten at temperatures less than about 30 95'C; more highly preferred compounds of this group being free from hydrophobic C, WO 00/52101 PCTIUS99/05795 10 chains having more than about x = 8 carbon atoms. This group includes especially polyalkylene glycol materials such as: A) Polyalkylene glycols and/or mixed polyalkylene glycols having average molecular weights of from about 150 to about 20,000, preferably between about 600 and 5 about 10,000, more preferably still from about 3,000 to about 6,000, e.g., about 4,000. Examples include: polyethylene glycols, preferably having molecular weights of from about 1,000 to about 9,000, more preferably from about 1,400 to about 5,000 (the term "PEG" may be used herein from time to time as an abbreviation for "polyethylene glycol); 10 polypropylene glycols, preferably having molecular weights of from about 600 to about 4,000; poly(tetramethylene glycol), preferably having molecular weights of from about 1,000 to about 10,000; mixed polyalkylene glycols such as poly(ethylene oxide / propylene oxide), for 15 example a poly(ethylene oxide / propylene oxide) having average molecular weight of about 1,100 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 0.15; a poly(ethylene oxide / propylene oxide) having average molecular weight of about 3,440 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 0.33; a poly(ethylene oxide / propylene oxide) having average molecular weight of about 1,100 20 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 0.15; a poly(ethylene oxide / propylene oxide) having average molecular weight of about 2,920 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 0.8; a poly(ethylene oxide / propylene oxide) having average molecular weight of about 13,333 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 3.0; a 25 poly(ethylene oxide / propylene oxide) having average molecular weight of about 8,750 and a ratio of ethylene oxide units to propylene oxide units (E/P) of about 5.0; mixed polyalkylene glycol block copolymers such as

HO[CH

2

CH

2 0]x[CH 2

CH(CH

3 )O]y[CH 2

CH

2 0]xoH and/or

HO[CH

2

CH(CH

3

)O],[CH

2

CH

2 0]x[CH 2

CH(CH

3 )O]yOH 30 wherein the sum of the y's ranges from about 15 to about 70, and the ratio of the sum of the x's to the sum of the y's is from about 1:10 to about 10:1, preferably from about 1:2 to WO 00/52101 PCT/US99/05795 11 about 1:1. Examples include materials made by BASF corporation and sold under the tradenames of Tetronic @ and Tetronic R @ respectively; (B) C 1

-C

8 alkylated polyalkylene glycols or poly(alkylene glycol) mono- and dialkyl ethers, RO(R 2 O)nH and/or RO(R 2 O),R; wherein each R is C 1

-C

8 alkyl, preferably methyl, 5 ethyl, propyl or butyl; each R 2 is a C 2

-C

4 alkylene group, and n ranges from 1 to about 200, with the percentage of polyalkylene glycol by weight of the compound preferably being greater than about 70%. Specific examples include:

RO[CH

2

CH(CH

3 0)]mH wherein R is methyl, ethyl, propyl or butyl, preferably methyl; and m is from about 1 to about 200 (molecular weight from about 90 to about 10 20,000);

RO(CH

2

CH

2 0),H, with each R being methyl, ethyl, propyl, or butyl, preferably methyl; and n being from about 2 to about 200 (molecular weight from about 120 to about 9,000), preferably from about 15 to about 150 (molecular weight from about 700 to about 6,700), more preferably from about 15 to about 100 (molecular weight from about 700 to 15 about 4,500); and/or

RO(CH

2

CH

2 0),R, with each R being methyl, ethyl, propyl or butyl; and n being from about 2 to about 200 (molecular weight from about 700 to about 6,700), more preferably from about 15 to about 100 (molecular weight from about 700 to about 4,500); (C) Polyalkoxylated materials having an average molecular weight of from about 20 200 to about 20,000 and the weight percent of the polyalkoxy portion being from about 50% to about 99%. Specific examples include Tetronic @ and Tetronic R @. Tetronic @ and Tetronic R @ are block polymeric materials manufactured by BASF Corp. Tetronic @ materials have the general formula:

CH

3 CH3

H(OCH

2

CH

2 )x(O CHCH 2 )y,/ (C H 2 CI0)y(CH2CH20)xH

NCH

2

CHI

2 N

H(OCI

2

CH

2 )x(OCHCH 2 )y/ (CH2CHO)y(C H 2 CH2O)xH

CI

3

CH

3 25 and Tetronic R @ materials have the general formula: WO 00/52101 PCT/US99/05795 12 CH3 CH3

H(OCHCH

2 )y(OCH 2

CH

2 )x /(CH 2

CH

2 0)x(CH 2 CHO)yH /NCH2CH2N\ H(OCHCH2)y(OCH2CH2)x (CH2CH 2 0)X(CH 2 CHO)yH 0H3 CH 3 wherein the sum of the y's ranges from about 8 to about 120, and the ratio of the sum of the x's to the sum of the y's is from about 1:10 to about 11:10, preferably from about 1:2 to about 1:1; 5 Specific examples are: polyethylene glycols with an average molecular weight of from about 600 to about 20,000; poly(tetramethylene glycols) with an average molecular weight of from about 1,000 to about 10,000; and poly(ethylene glycol) methyl ether with an average molecular weight of from about 500 to io about 20,000. Other analogs of water-soluble polymers of the above types may include varying numbers of butylene oxide moieties; or water-soluble polymers based on C 1

-C

4 alkylene oxide modifications of certain acetylenes, available from Air Products. 15 Another group of suitable water-soluble polymers for use herein is the poly(vinyl alcohols), especially those having molecular weight in the range from about 300 to about 20,000. Another preferred group of water-soluble polymers are water-soluble polymers which 20 include N as an aide, which are liquid or molten at temperatures less than about 95'C; more highly preferred compounds of this group being free from hydrophobic Cx chains having more than about 8 carbon atoms. This group includes especially: water-soluble polymers comprising as monomeric units vinylamides such as N vinylpyrrolidone and N-vinylacetamide as well as vinyl heterocycles such as N 25 vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine N-oxide; or poly-(N-isopropyl acrylamide), as described above for photo-oxidising agent (I). Most preferred water-soluble polymer compounds in this group in accordance with WO 00/52101 PCTIUS99/05795 13 this invention are polyvinylimidazole (PVI), or a copolymer of polyvinylpyrrolidone and polyvinylimidazole (PVPVI), most preferably polyvinylpyrrolidone (PVP). Preferably, these highly preferred water-soluble polymers have an average molecular weight of from 20,000 to 60,000. 5 Also suitable herein as the water-soluble polymer are mixtures of two or more of any of the foregoing water-soluble polymers. The photo-oxidising compound of photo-oxidising agent (II) herein generally comprise a 10 metal or metalloid selected from the group consisting of Si, Al, Ga, Ge and Sn, more preferably Si and Al, more preferably still, Si. The metal or metalloid, shown as "M" in the following structures, is bound to both to the chromophore and to ligands occupying axial positions, marked X or X' in these structures. x N N 15 Highly preferred are the compounds selected from the group consisting of x1N and mixtures thereof wherein X and Y can vary independently and represent bonded ligands and wherein preferred ligands include those identified in the section of the 20 specification "Ligand Examples" and in the Synthesis Examples hereinafter. The valence marked "*' in any of said structures, for example as shown in the Synthesis Examples, is bonded in axial position as indicated by said positions "X" or "Y". The term "ligand" herein most generally refers to an organic compound other than 25 phthalocyanine or naphthalocyanine (thus specifically excluding inorganic moieties such as WO 00/52101 PCT/US99/05795 14 water, -OH, -Cl etc. as in the precursor compound above). The ligand is an organic compound capable of binding axially to a Si, Al, Ga, Ge or Sn (preferably Si(IV)) phthalocyanine moiety. Si(IV) phthalocyanines comprising one organic axial ligand and one -OH ligand may be used herein, but preferably, when the metalloid is Si, the photo 5 oxidising compound will have two non-OH organic ligands. Preferred ligands herein have molecular weight of below about 500. The terms "bonded ligand" or "axial ligand" or "ligand in axial position" herein are used to distinguish ligand which is actually chemically bonded to the metal or metalloid, from 1o ligand which is simply present in physical admixture with the metal or metalloid compound. The term "axial" as in "axial position", or "axial ligand", is used herein to indicate a position of bonding with respect to a metal or metalloid. Specifically, in the case of 15 phthalocyanine compounds for example, the phthalocyanine chromophore occupies "equatorial positions" while all non-phthalocyanine ligands occupy "axial positions". In Si(IV) phthalocyanines there are two axial positions, whereas in Al phthalocyanines, there is only one. Thus, a "bonded axial ligand" is by definition a ligand, other than the chromophore, bonded to the metal or metalloid. 20 The term "nonbonded ligand" or "excess ligand" are used herein to distinguish ligand which is physically mixed with the metal or metalloid compound from ligand which is bonded. Preferred ligands herein can in general vary between the bonded ligand and the non 25 bonded or excess ligand. However it is preferred that all of said bonded and non-bonded ligands are selected from a group of like ligands. One such preferred group is the group consisting of polyhydroxy ligands. Another such preferred group is the group consisting of aminofunctional ligands. Also acceptable are mixtures of polyhydroxy ligands and aminofunctional ligands. 30 WO 00/52101 PCT/US99/05795 15 In highly preferred embodiment herein, all ligands are selected from the group consisting of in particular : O H O 7Me 0 H O bO O M e 0 * Me c (formula A) wherein a + b + c is from 0 to 16, preferably from 2 to 4; but also: 5 H d 0- * H ec O HO H wherein a+b+c+d is from 0 to 16, preferably 2 to 16; H O_10 Me Me 0 Me Me0 H Me H wherein a+b+c+d is from 0 to 16, preferably from 2 to 9; WO 00/52101 PCT/US99/05795 16 A0 A A Aco 0 A E 0 A Hb wherein A is independently selected from H and CH 3 and a,b,c, and d are numbers subject to an average molecular weight, M, of from 200 to 1000, preferably about 200-500, typically about 356; * eMe H{O bO 5 Me c wherein a+b+c is from 0 to 16, preferably 2 to 6; O - * a O Me H O b o O H c wherein a+b+c is from 0 to 16, preferably from 4 to 9; WO 00/52101 PCT/US99/05795 17 H b N 0 wherein a + b+ c is from 1 to 16, preferably 2 to 6; Me Me HO N OH -Me 0 HO OH MMe N OH Me M 5 WO 00/52101 PCT/US99/05795 18 Me Me-N N- Me 0 and mixtures thereof, wherein, when said ligand is nonbonded, a hydrogen atom completes the valence marked "*" in any of the above structures, and wherein, when the ligand is bonded to the photo-oxidising compound, the valence marked "*" in any of the above 5 structures is bonded to said metal or metalloid in an axial position. Preferred polyhydroxy ligands herein more generally are based on polyalkoxylated glycols or polyalkoxylated low molecular weight polyols. Such compounds include glycerol, pentaerythritol, and trimethylolpropane. Suitable alkoxylating agents include ethylene 10 oxide, propylene oxide or butylene oxide. Preferred polyhydroxy ligands have molecular weights below about 500 and are nonlimitingly illustrated by glycerol ethoxylates, glycerol propoxylates, glycerol ethoxylate/propoxylates, pentaerythritol ethoxylates, pentaerythritol propoxylates, 15 pentaerythritol ethoxylate/propoxylates, trimethylolpropane ethoxylates, trimethylolpropane propoxylates, and trimethylolpropane ethoxylate/propoxylates. Preferred aminofunctional ligands herein are non-limitingly illustrated by alkanolamines such as triethanolamine or tripropanolamine; or poly(alkoxylates) of such lower alkanolamines, such as 20 triethanolamine ethoxylate, triethanolamine propoxylate, or triethanolamine ethoxylate/propoxylate. Other suitable aminofunctional ligands include tetrahydroxyalkyl lower alkylene diamines, such as tetrahydroxypropyl ethylene diamine.

WO 00/52101 PCT/US99/05795 19 The photo-oxidising agent II as a whole herein can in general be solid or liquid. Preferred for many purposes are agents which are multiphasic, for example comprising a first solid phase, at ambient temperatures, of the water-soluble polymer, and a second phase, which may be solid or liquid, of the photo-oxidising component. Moreover, the photo-oxidising component and the water-soluble 5 polymer may be so well mixed that no clear phase boundary is observable by optical methods. Preferred agents can, for example, be a mixtures of non-charged hydrophobic photo-oxidising compounds and nonbonded ligands, wherein said nonbonded ligands are selected from the group consisting of compounds capable of binding axially to a Si, Al, Ga, Ge or Sn (preferably Si(IV)) 10 phthalocyanine moiety and said photo-oxidising compounds are selected from the group consisting of Si, Al, Ga, Ge and Sn phthalocyanines having a bonded ligand in at least one axial position and having solid form at ambient temperature in the absence of impurities. In this case, most suitably, an excess of ligand (nonbonded ligand) is maintained while a suitable photo-oxidising compound precursor is reacted with ligand to form the photo-oxidising compound. The nonbonded ligand 15 prevents crystallisation and the mixture of photo-oxidising compound and nonbonded ligand is combined with water-soluble polymer to form the agent II without crystallisation of ever first having occurred. The photo-oxidising agent II can preferred made by a process whereby the temperature is in the range from about -10'C 20 to about 50'C and said photo-oxidising compound is selected from the group consisting of nonsulfonated metal- or metalloid containing photo-oxidising compounds and said polymer is selected from the group consisting of at least partially water-soluble polymers, preferably the water-soluble polymers defined and 25 illustrated herein. In a preferred process, the photo-oxidising compound is a non-charged phthalocyanine compound of Silicon or Aluminium having one or more ligands bonded axially. The photo-oxidising agents I and II may be mixed with 30 conventional binders or carriers and/ or coated. Oxidative bleaching/ deinking WO 00/52101 PCT/US99/05795 20 The photo-oxidising agents herein can be used for oxidative bleaching or de-inking process for paper, pulp or yarn, which is to be understood to include all forms of bleaching of cellulosic raw material. 5 The oxidative pulp- or paper- or textile-bleaching or de-inking process preferably comprises the step of contacting the pulp, paper or yarn with an aqueous composition of the oxidative photo-oxidising agent. The photo-bleaching agent provides bleaching of the paper, pulp or yarn when the paper, 10 pulp or yarn is exposed to the sun or artificial light after application of the photo-oxidising agent. The improved solubility ensures that the photo-oxidising agent is delivered effectively throughout the bleaching solution, whilst the improved surface activity of the agents herein ensures a more efficient and effective bleaching. 15 The preferred bleaching compositions contains additional bleaching agents such as a peroxide source, such hydrogen peroxide(source). Inorganic perhydrate salts are a preferred source of hydrogen peroxide, which are normally used in the bleaching process, in the form of the alkali metal, preferably sodium salt at a level of from 0.05% to 20% by weight, more preferably from 1% to 15% by weight and most preferably from 2% to 8% 20 by weight of the pulp, paper or yarn. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate, preferably potassium peroxymonopersulfate, and persilicate salt. Sodium perborate can be in the form of the monohydrate of nominal formula NaBO 2

H

2

O

2 or the 25 tetrahydrate NaBO 2

H

2 0 2 .3H 2 0. Sodium percarbonate has a formula corresponding to 2Na 2

CO

3 .3H 2 0 2 , and is available commercially as a crystalline solid. Preferred bleaching agents also include chlorine-based bleaches. Also preferred is NaOCl or mixtures of NaOCl and H 2 0 2 . 30 WO 00/52101 PCTIUS99/05795 21 Also useful may be bleach activators, including in particular peroxyacid bleach or precursors thereto. Bleach activators may also be employed The preferred compositions for use in the bleaching processes herein are complexing 5 agents or chelating agents, including phosphonate-based compounds and carboxylate based compounds, such as EDTA, NTA and EDDS. Also preferred may be stabilisers. These include beta-hexahalofen. 10 It can be preferred however, to add a acidity source (e.g. H 2 S0 4 or H 2

SO

3 ) to the paper, pulp or yarn, prior to addition of the photo-oxidising agent and optionally other bleaching agents. Other solvents, such as alcohols may also be present when the photo-oxidising agents 1 herein are used to bleach paper, pulp or yarn. In a preferred embodiment, the photo-oxidising agents herein are applied to the pulp, paper or yarn which is to be dyed subsequently. 20 Hair bleaching compositions The photo-bleaching agents may also be used in hair-bleaching compositions to bleach the hair. These compositions commonly also employ a peroxygen bleach, as described above. The photo-bleaching agent provides bleaching of the hair when the hair is exposed to the sun or artificial light after application of the photo-oxidising agent. This provides a more 25 natural bleached colour to the hair. The improved surface activity of the agents herein ensures a more efficient and effective bleaching. 30 The hair-bleaching product may contain a hair conditioning agent.

WO 00/52101 PCT/US99/05795 22 Disinfecting and bactericidal, algicidal, herbicidal and fungicidal activity The photo-oxidising agents herein can be employed in bactericidal compositions, bactericidal, algicidal, herbicidal or fungicidal compositions. 5 The photo-oxidising agent herein can thus also be used as or present in a disinfectant. Generally, the photo-oxidising agent is used at a level of about 0.00 1 ppm to 2000 ppm, more preferably 0.01 or even 0.1 ppm to about 1000 ppm by weight of the water. 10 It may be preferred that additional bleaching agents are present, such as those mentioned in the previous section. A preferred additional ingredient can be a source of chlorine, in particular calcium is chloride. Another preferred additional ingredient can be benzoic acid or salt or derivatives thereof Preferred additional ingredients can also be a buffer solution in water/ alcohol or alcohol esters, for example: NaCl, NH4CI, Na2SO4 and cetyl/oleic alcohol mono-ester in water. 20 (Polymeric) quaternary ammonium salts can also be useful additional ingredients in the compositions of the invention. A preferred compound can be dimethylbenzylammonium chloride. Other ingredients can be benzoyl acids or derivatives thereof, benzene or benzene 25 derivatives, such as chlorobenzene, nitrilobenzene and benzene imidazol, and cyano derivatives. The disinfectants compositions can be used to disinfect any surface. They can also be used for example to disinfect the skin, including wounds. 30 WO 00/52101 PCT/US99/05795 23 The photo-oxidising agent is in particular useful in anti-microbial or disinfecting coatings. Examples are: 5 Low aqueous disinfecting composition Ingredients % (wt.) Formula Range Photo-oxidising agent 1 0.005-1.5

BPP

2 5-25 1,2-octanediol 0.1-7.0 MgAEI S 0.01- 0.8 MgAE 6

.

5 S 0.01-0.8

C

12 Dimethyl Amine Oxide 0.01-0.8

PEMULEN

3 0.05-0.20 perfume 0.01-1.5 water balance pH range from about 6 to about 8 1. Photo-oxidising agent I according to claim 2 and/ or agent II according to claim 3, whereby the ligand comprises compounds of formula A, above (p.16), and comprising 10 a Si group. 2. Other co-solvents which can be used herein together with the BPP, MPP, EPP and PPP primary solvents include various glycol ethers, including materials marketed under trademarks such as Carbitol, methyl Carbitol, butyl Carbitol, propyl Carbitol, hexyl Cellosolve, and the like. If desired, and having due regard for safety and odor for in 15 home use, various conventional chlorinated and hydrocarbon dry cleaning solvents may also be used. Included among these are 1,2-dichloroethane, trichloroethylene, isoparaffins, and mixtures thereof 3. As disclosed in U.S. Patents 4,758,641 and 5,004,557, such polyacrylates include homopolymers which may be crosslinked to varying degrees, as well as non- WO 00/52101 PCTIUS99/05795 24 crosslinked. Preferred herein are homopolymers having a molecular weight in the range of from about 100,000 to about 10,000,000, preferably 2000,000 to 5,000,000. Compositions for disinfecting of hard-surface. 5 Ingredients Weight % 47 48 49 50 51 52

C

12 alkyl sulphate 5 3 -- 1 1 2 nonionic C 12

E

6 6 4 8 3 4 3 butyl carbitol 4 -- 3 -- 2 sodium carbonate 7 9 4 9 5 3 Photo-oxidising agents 0.1 -- -- 0.1 -- 0.5 Photo-oxidising agent 2 -- 0.1 0.05 -- 0.3 water and adjuncts to 100 100 100 100 100 100 1. Photo-oxidising agent (I) according to claim 2. 2. Photo-oxidising agent (II) according to claim 3 whereby the ligand comprises compounds of formula A, above (p.16), and comprising a Si group. 10 The composition is applied to a surface which is then wiped clean, or the composition is applied to a wipe and then applied to the surface. Compositions to provide swimming pool disinfection Ingredients Weight % 53 54 55 56 sodium LAS -- 3 -- nonionic C 12

E

6 2 2 4 -

C

1 2 alkyl sulfate 4 -- -- sodium carbonate 8 7 10 30 Photo-oxidising agent 1 -- 0.01 -- 0.3 WO 00/52101 PCTIUS99/05795 25 Photo-oxidising agnet 2 0.1 -- -- 0.5 1. agent (I) according to claim 2 . 2. agent (II) according to claim 3. Typically usage concentrations is from about 10 ppm to about 10,000 ppm. The surfaces are dried in the presence of light, preferably natural sunlight, to achieve improved 5 photodisinfecting benefits. Absorbent articles The photo-bleaching agent may be comprised in disposable absorbent articles, for example to provide disinfecting of surfaces, or of the skin. For example, the photo-oxidising agent 10 can be present in cloths or wipes to clean and disinfect surfaces such as in kitchens or bath rooms. Alternatively, they can be present in wipes to clean the skin. They may also be present in absorbent articles which are applied to the skin, such as diapers, plasters, wound-dressings. 15 The articles may comprise one or more other ingredient which can help disinfecting of the skin or are beneficial to the skin, such as triacetin, benzalkonium salts, metal-containing compounds, in particular zinc-containing compounds, vitamins and cortisone's, and also compounds to soften the skin such as vaseline, glycerin, triethyleneglycol, lanolin, paraffin and another group of polymers extensively employed by pharmaceutical and cosmetic 20 manufactures, as also described herein. The disposable absorbent article preferably contains the photo-oxidising agent at a level of from 0.001 ppm to 1 % by weight of the article , more preferably from 0.01 ppm to o.5 %, most preferably from 0.1 ppm to 0.1 % by weight of the article. 25 Water-purification The photo-oxidising agent can also be used to purify water. This includes purification of water to provide potable water, but also for example water in pools.

WO 00/52101 PCT/US99/05795 26 Hereby, the photo-oxidising agent can not only act as a disinfectant or bactericidal, algicidal, herbicidal or fungicidal agent, as described above, but it can also react with and degrade organic pollutant. 5 The photo-oxidising agent is normally added in affective amounts to the polluted water, whereafter the water is exposed to sun-light or artificial light, depending on the application. When providing drinking water, it may be preferred that additional (sodium) lamps are positions in the water-purification kit. 1o Depending on the application, the reacted, degraded organic pollutants can be filtered out of the water, after the photo-oxidation is terminated. Generally, the photo-oxidising agent is used at a level of about 0.00 1 ppm to 2000 ppm, more preferably 0.01 or even 0.1 ppm to about 1000 ppm by weight of the water. 15 Highly preferred additional components for use hereby may be other bactericidal or fungicidal agents or algicidal agents and/ or additional bleaching agents, as described above. 20 Preferably, the photo-oxidising agent is used for water-purification at a pH of the water of at least 6. It may be preferred that the pH is at least 8 or even 9. Therefor it may be preferred that a alkaline buffer is used in combination with the photo-oxidising agent. 25 Photo-dynamic therapy The photo-oxidising agent herein can be useful to selectively destroy certain cells, including human or animal cells. In particular, the photo-oxidising agents can be used to 30 kill selectively tumor cells in the human or animal body. Thus, the photo-oxidising agents herein can be used to prepare compositions for use in photo-dynamic therapy.

WO 00/52101 PCTIUS99/05795 27 The photo-dynamic therapy generally comprises the step of administering the photo oxidising agent to the human or animal body and subsequently applying a light source to the body or body part to be treated, in particular a laser light. 5 Such methods are for example described in J.D. Spikes, Photchem.Photobiol. 43, 691 (1986). Administration can be topical or preferably intravenous, as forexample described in The U.S. Pharmacopoeia. . The topical applications may for example be gels, ointments, creams, preferably also comprising solvents including alcohols, 10 carriers, buffers, preservatives, cellulosic materilas, including starches and gums, alkali metal or alkali earth metal salts, or mixtures thereof. Intravenous compositions preferably comprise sterilized solvents such as water and preferably oils. 15 The agents can be administered preferably at levels up to 10.0 mg/ kg, preferably up to 5.0 mg/kg or even up to 1 mg/kg , and generally at a level of at least 0.01mg/kg or even 0.05 mg/ kg, by weight of the patient. Chemical oxidation reactions 20 The photo-oxidising agents herein can also be used for oxidising organic compounds comprising an allylic group, aromatic group, in particular a phenol group or cyanonitril group of said compounds. Spectral filer applications 25 The photo-oxidising agents herein can also be used to filter light. The precise light fractions filtered out will depend on the photo-oxidising compound or component present in the photo-oxidising agent. This can for example be useful to maximise the photo-synthesis of organisms 30 comprising chlorophyll, e.g. green plants. For example, a composition comprising the WO 00/52101 PCT/US99/05795 28 photo-oxidising agent can be applied on a transparent object surrounding the plants, such as glass or plastic of a green-house. Processes of preparing photo-oxidising agent II 5 Example I- 1 Synthesis of Silicon Phthalocyanine bis(1 PO/OH glycerol propoxylate) X N N.. N x Structure E-1 wherein bonded ligands, X, occupy axial positions and wherein these bonded ligands are 10 derived by deprotonating the ligand: H O a 0 H{O b O H OH a+b+c~3 fc To a 500 mL round bottom flask is added the ligand PO/OH glycerol propoxylate (Mn 266, 36g, 0.135 moles, Aldrich [25791-96-2]), followed by xylenes (170 mL). The mixture is heated to 170'C and is refluxed for 4 hours while water is removed by azeotropic 15 distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (0.711 g, 1.24 x 10-3 moles, Aldrich) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added (200 mL). The methylene chloride is extracted three times with 10 wt.% aqueous sodium chloride (200 mL). The methylene chloride is evaporated under reduced 20 pressure to give 6.8 g of the photo-oxidising compound Silicon Phthalocyanine bis(1 PO/OH glycerol propoxylate as a blue liquid. This compound is a crystalline solid when WO 00/52101 PCTIUS99/05795 29 pure. The liquid form contains excess (nonbonded) ligand. UV-Vis (dimethylformamide) 4,ax = 670, , = 217,200. Example 1-2 Synthesis of Silicon Phthalocyanine bis(3/4 EO/OH Pentaerythritol Ethoxylate) 5 This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: H HO H wherein a+b+c+d is about 3. 10 To a 500 mL round bottom flask is added the ligand 3/4 EQ/OH Pentaerythritol Ethoxylate (Mn 270, 24 g, Aldrich [30599-15-6]), followed by xylenes, (170 mL), and the mixture is heated to 1 70 0 C and refluxed for 4 hours while water is removed by azeotropic distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (0.50g, 8.7x10-4 moles, Aldrich) and the mixture is heated 15 again for 4.0 hours. The xylenes are evaporated off under reduced pressure and the blue oil is diluted with water (250 mL). Sodium sulfate (5.0 g) is added and the solution is transferred to a separatory funnel. The solution is extracted 3 times with methylene chloride (200 mL each time). The methylene chloride is evaporated under reduced pressure to give 1.2 g of the photo-oxidising compound Silicon Phthalocyanine bis(3/4 20 EQ/OH Pentaerythritol Ethoxylate) as a blue oil. This compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example I-3 Synthesis of Silicon Phthalocyanine bis( 15/4 EQ/OH Pentaerythritol Ethoxylate) WO 00/52101 PCT/US99/05795 30 This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: H r O c 0 H 5 wherein a+b+c+d is about 15. To a 500 mL round bottom flask is added 24 g of the ligand 15/4 EO/OH Pentaerythritol Ethoxylate (Mn 797), an Aldrich product [30599-15-6], followed by xylenes, 170 mL, and the mixture is heated to 170'C to a reflux for 4 hours while water is removed by azeotropic distillation. The flask is then charged with the photo-oxidising 10 compound precursor silicon phthalocyanine dihydroxide 0.50g (8.7x10-4 moles) and the mixture is heated again for 4.0 hours. The xylenes are evaporated off under reduced pressure and the blue oil is diluted with water 250 mL. Sodium sulfate 5.0 g is added and the solution is transferred to a separatory funnel. The solution is extracted 3 times with methylene chloride (200 mL). The methylene chloride is evaporated under reduced 15 pressure to give the photo-oxidising compound Silicon Phthalocyanine bis(15/4 EO/OH Pentaerythritol Ethoxylate) as a blue oil. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-4 Synthesis of Silicon Phthalocyanine bis(5/4 PO/OH Pentaerythritol propoxylate) 20 This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-I supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: WO 00/52101 PCT/US99/05795 31 H 0 M Me Me>0 Me 0-/ PC 0 00 H Me HH H wherein a+b+c+d is about 5. To a 500 mL round bottom flask is added the ligand 5/4 PO/OH Pentaerythritol propoxylate (Mn 426) 30g, an Aldrich product [9051-49-4], followed by xylenes 170 mL 5 and the mixture is heated to 170'C to a reflux for 4 hours while water is removed by azeotropic distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10 10% sodium chloride 200 mL. The methylene chloride is evaporated under reduced pressure to give the photo-oxidising compound compound Silicon Phthalocyanine bis(5/4 PO/OH Pentaerythritol propoxylate) as a blue liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. UV-Vis (dimethylformamide) k.max = 670, E = 209,500. 15 Example 1-5 Synthesis of Silicon Phthalocyanine bis(17/8 PO/OH Pentaervthritol propoxylate) This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: WO 00/52101 PCT/US99/05795 32 H 0 Me Me MeAO-M c O HM H wherein a+b+c+d is about 8.5. To a 500 mL round bottom flask is added the ligand 17/8 PO/OH Pentaerythritol propoxylate (Mn 629) 30g, an Aldrich product [9051-49-4], followed by xylenes 170 mL 5 and the mixture is heated to 170'C to a reflux for 4 hours while water is removed by azeotropic distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10 10% sodium chloride 200 mL. The methylene chloride is evaporated under reduced pressure to give Silicon Phthalocyanine bis(17/8 PO/OH Pentaerythritol propoxylate) as a blue liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-6 15 Synthesis of Silicon Phthalocyanine bis(Pentaerythritol propoxylate/ethoxylate) This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-I supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: WO 00/52101 PCT/US99/05795 33 A a O 0 A

O

H wherein each A can very independently and is selected from the group consisting of H and CH 3 ; and a,b,c and d are numbers provided that the number average molecular weight, M, is from about 201 to about 1001, preferably about 201-501, in the present 5 example, about 356. To a 500 mL round bottom flask is added the ligand Pentaerythritol propoxylate/ethoxylate (Mn 356) 30g, an Aldrich product [30374-35-7], followed by xylenes 170 mL and the mixture was heated to 170'C to a reflux for 4 hours while water is removed by azeotropic distillation. The flask is then charged with silicon phthalocyanine 10 dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10% sodium chloride 200 mL. The methylene chloride is evaporated under reduced pressure to give the photo-oxidising compound Silicon Phthalocyanine bis(Pentaerythritol propoxylate/ethoxylate) as a blue 15 liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-7 Synthesis of Silicon Phthalocyanine bis(lPO/OH Trimethylolpropane propoxylate) This photo-oxidising compound has the general structure shown in Structure E-1 20 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: WO 00/52101 PCTIUS99/05795 34 OH O aN 0 H O b o wherein a+b+c is about 3. To a 500 mL round bottom flask is added the ligand 1 PO/OH Trimethylolpropane propoxylate (Mn 308, 30g, Aldrich [25723-16-4]), followed by xylenes 170 mL and the 5 mixture is heated to 170'C to a reflux for 4 hours while water is removed by azeotropic distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10% sodium chloride 10 200 mL. The methylene chloride is evaporated under reduced pressure to give the photo oxidising compound Silicon Phthalocyanine bis(1PO/OH Trimethylolpropane propoxylate) as a blue liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-8 15 Synthesis of Silicon Phthalocyanine bis(2.5EO/OH Trimethylolpropane ethoxylate) This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: O H a O 0 H O b O O H c WO 00/52101 PCT/US99/05795 35 wherein a+b+c is about 7.5. To a 500 mL round bottom flask is added the ligand 2.5EO/OH Trimethylolpropane ethoxylate (Mn 450) 30g, an Aldrich product [50586-59-9], followed by xylenes 170 mL and the mixture is heated to 170'C to a reflux for 4 hours while water 5 is removed by azeotropic distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10% sodium chloride 200 mL. The methylene chloride is evaporated 10 under reduced pressure to give the photo-oxidising compound Silicon Phthalocyanine bis(2.5EO/OH Trimethylolpropane ethoxylate) as a blue liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-9 15 Synthesis of Silicon Phthalocyanine bis(1 EO/OH Triethanolamine ethoxylate) This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: H b 0 O OaH 0 0 Hec 20 wherein a+b+c is about 3. To a 500 mL round bottom flask is added the ligand 1 EO/OH Triethanolamine ethoxylate (M, 280, 30g, Aldrich [36936-60-4]), followed by xylenes (170 mL) and the mixture is heated to 170'C to a reflux for 4 hours while water is removed by azeotropic WO 00/52101 PCTIUS99/05795 36 distillation. The flask is then charged with the photo-oxidising compound precursor silicon phthalocyanine dihydroxide 0.5g (8.7x10-4 moles) and the mixture is heated again for 3.5 hours. The xylenes are evaporated off under reduced pressure and methylene chloride is added 200 mL. The methylene chloride is extracted three times with 10% sodium chloride 5 200 mL. The methylene chloride is evaporated under reduced pressure to give the photo oxidising compound Silicon Phthalocyanine bis(1 EO/OH Triethanolamine ethoxylate) as a blue liquid. This photo-oxidising compound is a crystalline solid when pure, and the liquid (oil) form contains excess (nonbonded) ligand. Example 1-10 10 Preparation of silicon phthalocyanine-di-(2-((2-(Dimethylamino)ethyl) methylamino)ethanol). This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions, are derived from 2 -((2-(Dimethylamino)ethyl)-methylamino)ethanol and have the structure: Me Me-N N -Me 0 15 wherein the asterisk (*) shows the point of bonding to Si(PC). A mixture of the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (0.25 g, 0.44 mmole), the ligand 2-((2-(Dimethylamino)ethyl)-methylamino)ethanol (9.8 g, 67 mmole, 20 Aldrich) and xylenes (175 mL) is heated to reflux over 1.5 hr. The solution is continued at reflux for 2 hr. while water is removed by azeotropic distillation. The reaction mixture is then cooled and the solvent removed in vacuo. The resulting crude oil is dissolved in dimethylformamide (50 mL) and is added to water (800 mL) over about 0.5 hr. A blue solid forms. This is collected by filtration, and dried under vacuum at 80C'. This is the WO 00/52101 PCTIUS99/05795 37 photo-oxidising compound silicon phthalocyanine-di-(2-((2-(Dimethylamino)ethyl) methylamino)ethanol), in solid microcrystalline form, without significant amounts of excess (nonbonded) ligand. The crystal size distribution is estimated as 100% < 30 micron, mean size < 10 micron. 5 Example I-11 Preparation of silicon phthalocyanine-di-(triisopropanolamine). This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-1 supra. However, bonded ligands, X, which occupy axial positions, are derived from triisopropanolamine and have the structure: Me Me HO OH N Me 0 10 wherein the asterisk (*) shows the point of bonding to Si(PC). A mixture of the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (0.25 g, 0.44 mmole), the ligand triisopropanolamine (12.8 g, 67 mmole, Aldrich) and xylenes (175 mL) is heated to reflux over 1.5 hr. The solution is continued at reflux for 2 hr. while water is 15 removed by azeotropic distillation. The reaction mixture is then cooled and the solvent removed in vacuo. The resulting crude oil is dissolved in dimethylformamide (50 mL) and is added to water (800 mL) over about 0.5 hr. A blue solid forms. This is collected by filtration, and dried under vacuum at 80C'. This is the photo-oxidising compound silicon phthalocyanine-di-(triisopropanolamine), in solid microcrystalline form, without significant 20 amounts of excess (nonbonded) ligand. The crystal size distribution is estimated as 100% < 30 micron, mean size < 10 micron. Example 1-12 Preparation of silicon phthalocyanine-di-(triethanolamine).

WO 00/52101 PCTIUS99/05795 38 This photo-oxidising compound has the general structure shown in Structure E-1 of Example I-I supra. However, bonded ligands, X, which occupy axial positions, are derived from triethanolamine and have the structure: HO O H 0 5 wherein the asterisk (*) shows the point of bonding to Si(PC). A mixture of the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (0.25 g, 0.44 mmole), the ligand triethanolamine (10 g, 67 mmole, anhydrous, Aldrich) and xylenes (175 mL) is heated to reflux over 1.5 hr. The solution is continued at reflux for 2 hr. while water is removed by azeotropic distillation. The reaction mixture is then cooled and the 10 solvent removed in vacuo. The resulting crude oil is dissolved in dimethylformamide (50 mL) and is added to water (800 mL) over about 0.5 hr. A blue solid forms. This is collected by filtration, and dried under vacuum at 80 . This is the photo-oxidising compound silicon phthalocyanine-di-(triethanolamine), in solid microcrystalline form, without significant amounts of excess (nonbonded) ligand. The crystal size distribution is 15 estimated as 100% < 30 micron, mean size < 10 micron. UV-Vis (dimethylformamide) Xmax =670, , = 228,300. Example 1-13 Synthesis of Silicon Phthalocyanine bis(tetrahydroxypropyl ethylenediamine) This photo-oxidising compound has the general structure shown in Structure E-1 20 of Example I-I supra. Bonded ligands, X, which occupy axial positions, have the structure: WO 00/52101 PCTIUS99/05795 39 Me HO Me OH Me OH 0 Me wherein the asterisk (*) shows the valence or point of attachment to Si(PC). Assemble a 500 mL, 3-necked round bottom flask fitted with a Dean-Stark drying apparatus, reflux condenser, argon inlet, magnetic stir bar, internal thermometer, Therm-o 5 watchTM temperature control means and heating mantle. Charge with 300 mL xylenes (0.1 L xylenes/mmol silicon phthalocyanine dihydroxide) and the ligand Quadrol T M polyol (common chemical name: tetrahydroxypropyl ethylenediamine, BASF, 56g, 192 mmol). Under argon and with magnetic stirring, heat to xylene reflux temperature (approximately 140'C) for 4 hours during which time the solvent and starting material are dried via 10 azeotropic distillation with xylenes. Allow the reaction to cool to room temperature over 16 hours under argon. Add the photo-oxidising compound precursor silicon phthalocyanine dihydroxide (1.7 g, 3 mmol, Aldrich) to the reaction. Return the reaction to reflux for 4 hours during which time water is removed via azeotropic distillation with xylenes. The reaction mixture is a green/blue solution with some dark solids collected on 15 the flask walls. Cool the reaction mixture to room temperature. Transfer the solution to a 1-liter, 1-necked round bottom flask and remove xylenes via the rotary evaporator. Dilute the resulting green/blue oil with 200 mL methylene chloride. Wash the methylene chloride solution three times with aqueous sodium chloride (200 mL, 10 wt. %.) Discard aqueous washes. Concentrate the organic layer on a rotary evaporator resulting in an aqua blue oil. 20 Remove final traces of solvent from the sample by vacuum drying (using a vacuum pump) at 80'C for 16 hours with magnetic stirring. Final product is a highly viscous aqua blue liquid. Sample is analyzed by proton NMR in deuterated chloroform and the percent silicon is measured via AAS. Final recovery is 35.7 g. This is the photo-oxidising compound Silicon Phthalocyanine bis(tetrahydroxypropyl ethylenediamine), as an oil WO 00/52101 PCTIUS99/05795 40 containing excess ligand. The content of the photo-oxidising compound in the oil is consistent with an Si content (activity) of 8.0 wt%. Example 1-14 Photo-oxidising System consisting essentially of a PEG-4000 Blend with Silicon 5 Phthalocyanine bis(1 PO/OH glycerol propoxylate) and nonbonded ligand, glycerol propoxylate To a glass jar is added a 15.0 g sample, in the form of an oil, of silicon phthalocyanine bis(1 PO/OH glycerol propoxylate) having an activity of 16.8 wt% (the remainder is nonbonded ligand, glycerol propoxylate) followed by 79.4 g of melted PEG 10 4000 polymer. The polymer is melted on a hot plate at 70'C. The mixture is stirred with a magnetic bar with heating for 5 minutes to give a homogeneous solution and is then cooled to room temperature. The resulting blue solid is ground to a powder and is ready for use. The final composition of the photo-oxidising agent delivery system is: Photo-oxidising compound 2.7%, Glycerol propoxylate nonbonded ligand 13.2%, PEG-4000 polymer 15 84.1%. Example 1-15 Isolation of Solid Silicon Phthalocyanine bis(glycerol propoxylate) For comparison with Example I-1 wherein the photo-oxidising compound silicon phthalocyanine bis(glycerol propoxylate) is obtained as an oil having present nonbonded 20 ligand, this photo-oxidising compound can be isolated as a solid. The present example illustrates conversion to the solid. Charge a 12-liter, 1-necked round bottom flask, fitted with a magnetic stirrer and argon inlet, with 7.05 g of the photo-oxidising compound silicon phthalocyanine bis(glycerol propoxylate) containing excess glycerol propoxylate ligand (prepared 25 comparably to Example I-1). Dilute with 7 L deionized water and stir under argon for 1 hour. Collect the water insoluble material by vacuum filtration and allow to air dry in the hood overnight. Recovery is 0.95 g. The photo-oxidising compound has solid form and has been substantially freed from nonbonded ligand. The solid is still somewhat tacky. Additional material remains on the flask wall. To determine the amount of photo 30 oxidisingcompound remaining in the flask, tare the flask, rinse with methylene chloride to remove all remaining product, allow to dry and reweigh. The difference in the weight of WO 00/52101 PCT/US99/05795 41 the flask accounts for 0.28 g of additional silicon phthalocyanine bis(glycerol propoxylate). Total recovery is 1.23 g or 17.5%. Total isolated yield is 66.1% based on 1.0 g (1.74 mmol) of silicon phthalocyanine bis(hydroxide) starting material. Conventional crystallizations can be used to further improve the quality. 5

Claims (17)

1. A composition for bleaching pulp, paper or yarn comprising a photo-oxidising agent I) or II) or mixtures thereof, 5 photo-oxidising agent I) being a polymeric component and a photo-oxidising component, integrated with one another, whereby the weight ratio of the polymeric component to the photo-oxidising component is from 1:1 to 1000:1; 10 photo-oxidising agent (II) being a mixture of a water-soluble polymer and a photo oxidising component being a mixture of non-charged hydrophobic photo-oxidising compounds and nonbonded ligand selected from the group consisting of compounds capable of binding axially to a Si, Al, Ga, Ge or Sn phthalocyanine moiety and said photo-oxidising compounds are selected from the group consisting of Si, Al, Ga, Ge 15 and Sn phthalocyanines having a bonded ligand in at least one axial position and having solid form at ambient temperature in the absence of impurities.

2. A composition of claim 1 wherein the photo-oxidising agent (I) comprises from 90% to 99.9% by weight of the agent of the polymeric component and from 0.1% to 10% by 20 weight of the agent of the photo-oxidising component; wherein the polymeric compound has an average number molecular weight of from 500 to 1,000,000 and preferably comprises polymerised monomeric units whereof at least 50% of the units comprise a di-polar, aprotic group, preferably being N vinylpyrrolidone, N-vinylacetamide, N-vinylimidazole, N-vinyloxazolidone, N 25 vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine-N-oxide, N-alkyl pyrrolidinone, preferably N- methyl or N-octyl pyrrolidinone; and wherein the photo-oxidising compound is preferably a metallo phthalocyanine, preferably zinc or aluminium metallo phthalocyanine. WO 00/52101 PCT/US99/05795 43

3. A composition according to claim 1 or 2 wherein the photo-bleaching agent (II) comprises the water-soluble polymer and said photo-oxidising compound at a ratio by weight of from about 2,500:1 to about 1:10; wherein said nonbonded ligand and said photo-oxidising compound are at a ratio by 5 weight of from about 100:1 to about 1:1,000, and wherein said photo-oxidising component consists essentially of: (A) a metal or metalloid selected from Si and Al; (B) a chromophore selected from phthalocyanine and naphthalocyanine, provided said photo-oxidising compound is not thereby rendered substantially soluble in water and 10 (C) one or two of said bonded ligands, in axial position.

4. A hair-bleaching composition comprising the photo-oxidising agent as defined in any of claims 1 to 3. 15

5. Use of a photo-bleaching agent defined in any of claims 1 to 3 for bleaching of pulp, paper or yarn or hair.

6. Method for dyeing fabrics or paper or components thereof comprising the step of contacting the fabric or paper or components thereof with a composition or photo 20 oxidising agent as defined in any of claims I to 3 prior to the dying step.

7. A disinfectant composition comprising the photo-oxidising agent as defined in any of claims 1 to 3. 25

8. A bactericidal algicidal, herbicidal or fungicidal compositions comprising a photo oxidising agent as defined in any of claims 1 to 3.

9. Coating agent comprising the photo-oxidising agent as defined in any of claims 1 to 30

10. Use of a photo-oxidising agent as defined in any of claims 1 to 3 as a disinfectant. WO 00/52101 PCT/US99/05795 44

11. Use of a photo-oxidising agent as defined in any of claims 1 to 3 for preparation of a composition for the reduction of the activity of micro-organisms or the growth of plants, fungi and/ or algae. 5

12. An absorbent article comprising the photo-oxidising agent as defined in any of claims 1 to 3, the article preferably being in the form of a bandage, plaster, wound dressing, wipe, tissue, tampon, catamenial or a diaper. 10

13. Use of a photo-oxidising agent as defined in any of claims 1 to 3 for water purification by degradation of organic components in the water and/ or reduction of the activity of micro-organisms in the water, preferably for purification of drinking water.

14. Use of a photo-oxidising agent as defined in any of claims 1 to 3 for preparation 15 of a composition for destruction of human or animal cells.

15. Use of a photo-oxidising agent as defined in any of claims 1 to 3 for preparation of a composition for photo-dynamic therapy. 20

16. Use of a photo-oxidising agent as defined in any of claims 1 to 3 for oxidation of organic compounds comprising an allyl group, aromatic group or cyanonitril group.

17. Use of a photo-oxidising agent as defined in any of claims 1 to 3 as a spectral filter, preferably for increasing the photo synthesis of plants. 25 30