WO2000052101A1 - Composition comprenant un agent photo-oxydant et utilisations de cet agent - Google Patents

Composition comprenant un agent photo-oxydant et utilisations de cet agent Download PDF

Info

Publication number
WO2000052101A1
WO2000052101A1 PCT/US1999/005795 US9905795W WO0052101A1 WO 2000052101 A1 WO2000052101 A1 WO 2000052101A1 US 9905795 W US9905795 W US 9905795W WO 0052101 A1 WO0052101 A1 WO 0052101A1
Authority
WO
WIPO (PCT)
Prior art keywords
photo
oxidising
agent
water
oxidising agent
Prior art date
Application number
PCT/US1999/005795
Other languages
English (en)
Inventor
Rafael Ortiz
David Johnathan Kitko
Michael Eugene Burns
Stephen Wayne Heinzman
Alan David Willey
Brian Jeffreys
James Charles Theophile Roger Burckett-St. Laurent
Phillip Kyle Vinson
Trace Wendell De Guzman Trajano
Original Assignee
Case Western Reserve University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Case Western Reserve University filed Critical Case Western Reserve University
Priority to BR9917226-7A priority Critical patent/BR9917226A/pt
Priority to AU30948/99A priority patent/AU3094899A/en
Priority to MXPA01008952A priority patent/MXPA01008952A/es
Priority to EP99912606A priority patent/EP1159354A1/fr
Priority to ARP000100956A priority patent/AR031824A1/es
Publication of WO2000052101A1 publication Critical patent/WO2000052101A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/32—Bleaching agents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
    • A61K41/0071—PDT with porphyrins having exactly 20 ring atoms, i.e. based on the non-expanded tetrapyrrolic ring system, e.g. bacteriochlorin, chlorin-e6, or phthalocyanines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1063—Bleaching ; Apparatus therefor with compounds not otherwise provided for, e.g. activated gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • 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.
  • porphyrin and phthalocyanine photo-bleaching compounds 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 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 hydrogen peroxide, formed in this series of reactions, are also oxidative species.
  • porphyrins or porphyrin-like compounds examples include haematoporphyrin, chlorophyll, chlorin, oxo-chlorins, pheophorbide, pyropheophorbide, benzoporphyrins, tetra- arylporphyrin, zinc tetraphenylporphyrin, tripyrroledimethane-derived expanded porphyrins.
  • phthalocyanines and naphthalocyanines include zinc, aluminum, indium, silicon, and gallium phthalocyanines and naphthalocyanines, the most common being the zinc and aluminium phthalocyanines.
  • 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 limitation to the use of some of these more water-soluble photo-bleaches can be their poor surface-activity.
  • phthalocyanine, naphthalocyanines, and porphyrin photo-bleaching compounds arises from the fact that these are not water soluble, in particular when the parent rings are substituted solely with hydrogen.
  • phthalocyanine derivatives have been modified with various solubilising substituents, for example described in EP-119746, EP-379312, EP-553608, EP-596187 and EP-692947.
  • substituents for example described in EP-119746, EP-379312, EP-553608, EP-596187 and EP-692947.
  • a problem relating to the introduction of (high numbers of) substituent groups to the photo-bleaching compound is that the photo- 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 cost. These impurities may also introduce undesirable colouring. Yet another limitation of most of these substituted compounds is that introduction of solubilising substituent groups 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.
  • co-pending application GB 9719779.2 provides improved photo-bleaching agents with the desired absorption spectrum, which are water-soluble and which have an 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 as agent II, to provide an improved photo-bleaching performance
  • 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).
  • 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. 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.
  • the new oxidising agents are for example very useful for bleaching of pulp, paper or yarn. Also, they are useful in hair-bleaching. 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.
  • 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):
  • 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;
  • - photo-oxidising agent (II) being a mixture of a water-soluble polymer and a photo- o 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 5 at ambient temperature in the absence of impurities.
  • Photo-oxidising Agent (I) o
  • 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 specific polymeric components and one or more photo-oxidising components integrated with one another, as described herein
  • 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
  • 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%o 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 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 polymeric component of the photo-oxidising agent (I) of the invention preferably comprises polymerised monomeric units which comprise di-polar, aprotic groups 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.
  • 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.
  • vinylamides such as N-vinylpyrrolidone and N-vinylacetamide
  • vinylheterocycles such as N-vinylimidazole, N- vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine-N-oxide.
  • 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, o palmityl, phenoxyethyl, stearylacrylate.
  • diethylaminoethylacrylate, dimethylaminoethylacrylate, dimethylaminopropylacrylate, and choline esters of acrylic or methacrylic acid are also included.
  • acrylamide or methacrylamide and their various N- substituted derivatives including N-methylol-acrylamide, N,N- dimethylaminopropylacrylamide, N,N,N-trimethylammoniumpropylacrylamide, N,N- 5 diethylaminopropylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N- undecylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid.
  • vinyl esters such as vinyl acetate, vinyl propionate, vinyllaurate, neooctanoic acid vinylester, neononanoic acid vinylester, neodecanoic acid vinylester.
  • vinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene.
  • unsaturated o acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or their respective anhydride or esters.
  • polymeric compounds for photo-oxidising agent (I) are polyvinylimidazole (PNI), or a copolymer of polyvinylpyrrolidinone and polyvinylimidazole (PVPNI), most preferably polyvinylpyrrolidinone (PVP).
  • PNI polyvinylimidazole
  • PVPNI polyvinylimidazole
  • these highly preferred polymeric compounds have an average molecular weight of from 20,000 to 60,000.
  • 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.
  • 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 "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.
  • 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 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.
  • 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.
  • 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 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- pending application GB9719779.2.
  • the polymeric compound of photo-bleaching agent (II) is a water-soluble polymer.
  • 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 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.
  • Water-soluble polymers selected for use herein preferably have solubility parameters in the range from about 15 to about 42 MPa 1 2 , preferably 16 to 35 MPa 1 2 , more preferably 17 to 30 MPa 1 2 .
  • 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 MPa 1/2 .
  • 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.
  • 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.
  • the water-soluble polymers may optionally include limited proportions of hydrophobic moieties such as relatively short, e.g., C C 8 , preferably C ⁇ -C alkyl moieties, optionally in amide, ether or ester side-chains, provided that they remain water-soluble.
  • hydrophobic moieties such as relatively short, e.g., C C 8 , preferably C ⁇ -C 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 o 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.
  • 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.
  • This group includes especially polyalkylene glycol materials such as
  • 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), 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 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,
  • RO(CH 2 CH 2 O) n 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 about 4,500), and/or
  • RO(CH 2 CH 2 O) n 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),
  • Tetronic ® and Tetronic R ® Tetronic ® and Tetronic R ® are block polymeric materials manufactured by BASF Corp Tetronic ® materials have the general formula
  • Tetronic R ® materials have the general formula 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; 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 about 20,000.
  • water-soluble polymers of the above types may include varying numbers of butylene oxide moieties; or water-soluble polymers based on C ⁇ -C alkylene oxide modifications of certain acetylenes, available from Air Products.
  • 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.
  • water-soluble polymers are water-soluble polymers which include N as an amide, which are liquid or molten at temperatures less than about 95°C; more highly preferred compounds of this group being free from hydrophobic C x 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- 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).
  • vinylamides such as N- vinylpyrrolidone and N-vinylacetamide
  • vinyl heterocycles such as N- vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine
  • Most preferred water-soluble polymer compounds in this group in accordance with this invention are polyvinylimidazole (PNI), or a copolymer of polyvinylpyrrolidone and polyvinylimidazole (PVPNI). most preferably polyvinylpyrrolidone (PNP).
  • PNI polyvinylimidazole
  • PVPNI polyvinylimidazole
  • PNP polyvinylpyrrolidone
  • these highly preferred water-soluble polymers have an average molecular weight of from 20,000 to 60,000.
  • 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 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 and Y can vary independently and represent bonded ligands and wherein preferred ligands include those identified in the section of the 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".
  • ligand herein most generally refers to an organic compound other than phthalocyanine or naphthalocyanine (thus specifically excluding inorganic moieties such as 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(IN)) phthalocyanine moiety Si(IN) phthalocyanines comprising one organic axial ligand and one -OH ligand may be used herein, but preferably, when the metalloid is Si, the photo- oxidising compound will have two non-OH organic ligands
  • Preferred ligands herein have molecular weight of below about 500
  • 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 ligand which is simply present in physical admixture with the metal or metalloid compound
  • 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 phthalocyanine compounds for example, the phthalocyanine chromophore occupies
  • a "bonded axial ligand” is by definition a ligand, other than the chromophore, bonded to the metal or metalloid
  • 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- 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 In highly preferred embodiment herein, all ligands are selected from the group consisting of in particular :
  • a+b+c+d is from 0 to 16, preferably 2 to 16;
  • a+b+c+d is from 0 to 16, preferably from 2 to 9; 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 n of from 200 to 1000, preferably about 200-500, typically about 356;
  • a+b+c is from 0 to 16, preferably 2 to 6;
  • a+b+c is from 0 to 16, preferably from 4 to 9; wherein a + b+ c is from 1 to 16, preferably 2 to 6;
  • 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 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, pentaerythritol ethoxylate/propoxylates, trimethylolpropane ethoxylates, trimethylolpropane propoxylates, and trimethylolpropane ethoxylate/propoxylates
  • alkanolamines such as triethanolamine or t ⁇ propanolamine. or poly(alkoxylates) of such lower alkanolamines, such as triethanolamine ethoxylate, triethanolamine propoxylate, or triethanolamine ethoxylate/propoxylate
  • Suitable aminofunctional ligands include tetrahydroxyalkyl lower alkylene diamines, such as tetrahydroxypropyl ethylene diamme
  • the photo-oxidising agent II as a whole herein can m 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-oxidismg component and the water-soluble 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 S ⁇ (IV)) 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 m the absence of lmpunties
  • an excess of ligand (nonbonded ligand) is maintained while a suitable photo-oxidismg compound precursor is reacted with ligand to form the photo-oxidising compound
  • the nonbonded ligand 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-oxidismg agent II can preferred made by a process whereby the temperature is m the range from about -10°C to about 50°C and said photo-oxidismg compound is selected from the group consisting of nonsulfonated metal- or metalloid- containing photo-oxidismg compounds and said polymer is selected from the group consisting of at least partially water-soluble polymers, preferably the water-soluble polymers defined and illustrated herein.
  • the photo-oxidismg compound is a non-charged phthalocyanine compound of Silicon or Aluminium having one or more ligands bonded axially.
  • the photo-oxidismg agents I and II may be mixed with conventional binders or carriers and/ or coated.
  • Oxidative bleaching/ deinking 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.
  • 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, 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.
  • the preferred bleaching compositions contains additional bleaching agents such as a peroxide source, such hydrogen peroxide(source).
  • a peroxide source such as 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%> by weight of the pulp, paper or yarn.
  • 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 NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Sodium percarbonate has a formula corresponding to 2Na2CO3.3H2O2, 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 O 2 . Also useful may be bleach activators, including in particular peroxyacid bleach or precursors thereto. Bleach activators may also be employed
  • compositions for use in the bleaching processes herein are complexing agents or chelating agents, including phosphonate-based compounds and carboxylate- based compounds, such as EDTA, NTA and EDDS.
  • stabilisers include beta-hexahalofen.
  • a acidity source e.g. H 2 SO 4 or H 2 SO 3
  • H 2 SO 4 or H 2 SO 3 a acidity source
  • solvents such as alcohols may also be present when the photo-oxidising agents herein are used to bleach paper, pulp or yarn.
  • the photo-oxidising agents herein are applied to the pulp, paper or yarn which is to be dyed subsequently.
  • 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 natural bleached colour to the hair.
  • the improved surface activity of the agents herein ensures a more efficient and effective bleaching.
  • the hair-bleaching product may contain a hair conditioning agent. 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.
  • the photo-oxidising agent herein can thus also be used as or present in a disinfectant.
  • the photo-oxidising agent is used at a level of about 0.001 ppm to 2000 ppm, more preferably 0.01 or even 0.1 ppm to about 1000 ppm by weight of the water.
  • 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 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, NH4C1, Na2SO4 and cetyl/oleic alcohol mono-ester in water.
  • Polymeric quaternary ammonium salts can also be useful additional ingredients in the compositions of the invention.
  • a preferred compound can be dimethylbenzylammonium chloride.
  • ingredients can be benzoyl acids or derivatives thereof, benzene or benzene 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.
  • the photo-oxidising agent is in particular useful in anti-microbial or disinfecting coatings.
  • 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- 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.
  • such polyacrylates include homopolymers which may be crosslinked to varying degrees, as well as non- 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 are provided.
  • Photo-oxidising agent (I) according to claim 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.
  • 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.
  • Photo-oxidising agent 1 0.01 _- 0.3 Photo-oxidising agnet 2 0.1 — ⁇ 0.5
  • agent (I) according to claim 2 .
  • agent (II) according to claim 3.
  • Typical 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.
  • the photo-bleaching agent may be comprised in disposable absorbent articles, for example to provide disinfecting of surfaces, or of the skin.
  • the photo-oxidising agent 0 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.
  • 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 o manufactures, as also described herein.
  • ingredient which can help disinfecting of the skin or are beneficial to the skin
  • vaseline glycerin, triethyleneglycol, lanolin, paraffin and another group of polymers extensively employed by pharmaceutical and cosmetic o 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. 5
  • 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.
  • 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.
  • 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.
  • additional (sodium) lamps are positions in the water-purification kit.
  • the reacted, degraded organic pollutants can be filtered out of the water, after the photo-oxidation is terminated.
  • the photo-oxidising agent is used at a level of about 0.001 ppm to 2000 ppm, more preferably 0.01 or even 0.1 ppm to about 1000 ppm by weight of the water.
  • 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.
  • 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.
  • the photo-oxidising agent herein can be useful to selectively destroy certain cells, including human or animal cells.
  • the photo-oxidising agents can be used to 0 kill selectively tumor cells in the human or animal body.
  • the photo-oxidising agents herein can be used to prepare compositions for use in photo-dynamic therapy.
  • 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.
  • 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, 0 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.
  • 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 O.Olmg/kg or even 0.05 mg/ kg, by weight of the patient.
  • 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.
  • 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.
  • a composition comprising the photo-oxidising agent can be applied on a transparent object surrounding the plants, such as glass or plastic of a green-house.
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example 1-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: H
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example 1-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand:
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example 1-1 supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand:
  • 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 n is from about 201 to about 1001, preferably about 201-501, in the present example, about 356.
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand: wherein a+b+c is about 3.
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand:
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra. However, bonded ligands, X, which occupy axial positions are derived by deprotonating the ligand:
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra.
  • bonded ligands, X which occupy axial positions, are derived from 2-((2-(Dimethylamino)ethyl)-methylamino)ethanol and have the structure:
  • 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-(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.
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra.
  • bonded ligands, X which occupy axial positions, are derived from triisopropanolamine and have the structure:
  • This photo-oxidising compound has the general structure shown in Structure E-l of Example I-l supra.
  • Bonded ligands, X which occupy axial positions, have the structure:
  • Photo-oxidising System consisting essentially of a PEG-4000 Blend with Silicon 5 Phthalocyanine bis(l PO/OH glycerol propoxylate) and nonbonded ligand. 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.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Biochemistry (AREA)
  • Textile Engineering (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Birds (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cosmetics (AREA)

Abstract

Cette invention se rapporte à certaines compositions comprenant des agents photo-oxydants spécifiques, qui sont constitués par un mélange d'un composant photo-oxydant choisi et de polymères sélectionnés, ayant des performances photo-oxydantes accrues, notamment en raison d'une plus grande solubilité et activité de surface et d'une meilleure absorption de la lumière. Cette invention concerne également un certain nombre d'utilisations de ces agents, telles que la décoloration des cheveux et le blanchiment du papier, de la pâte à papier et des fils textiles; l'épuration de l'eau; des tâches de désinfection; et la thérapie photo-dynamique.
PCT/US1999/005795 1999-03-05 1999-03-17 Composition comprenant un agent photo-oxydant et utilisations de cet agent WO2000052101A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9917226-7A BR9917226A (pt) 1999-03-05 1999-03-17 Composição compreendendo um agente de foto-oxidação e usos do agente
AU30948/99A AU3094899A (en) 1999-03-05 1999-03-17 A composition comprising a photo-oxidising agent and uses of the agent
MXPA01008952A MXPA01008952A (es) 1999-03-05 1999-03-17 Una composicion que comprende un agente foto-oxidante y usos del agente.
EP99912606A EP1159354A1 (fr) 1999-03-05 1999-03-17 Composition comprenant un agent photo-oxydant et utilisations de cet agent
ARP000100956A AR031824A1 (es) 1999-03-17 2000-03-03 Composicion para blanquear pulpa, papel o hilo, composicion blanqueadora del cabello, uso de un agente foto- blanqueador para blanquear pulpa, papel o hilo o cabello, metodo para colorear telas y composicion desinfectante, composiciones bactericidas, alguicidas, herbicidas y fungicidas y agente de r

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12300599P 1999-03-05 1999-03-05
US60/123,005 1999-03-05

Publications (1)

Publication Number Publication Date
WO2000052101A1 true WO2000052101A1 (fr) 2000-09-08

Family

ID=22406179

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US1999/005795 WO2000052101A1 (fr) 1999-03-05 1999-03-17 Composition comprenant un agent photo-oxydant et utilisations de cet agent
PCT/US2000/005408 WO2000052122A1 (fr) 1999-03-05 2000-03-01 Compositions de detergent contenant des systemes d'apport d'agent de photoblanchiment

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2000/005408 WO2000052122A1 (fr) 1999-03-05 2000-03-01 Compositions de detergent contenant des systemes d'apport d'agent de photoblanchiment

Country Status (6)

Country Link
EP (2) EP1159354A1 (fr)
AR (1) AR022825A1 (fr)
AU (2) AU3094899A (fr)
BR (2) BR9917226A (fr)
MX (2) MXPA01008952A (fr)
WO (2) WO2000052101A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1588691A1 (fr) * 2004-04-22 2005-10-26 L'oreal Composition pour la déformation permanente des cheveux contenant un réducteur et un photooxydant
KR100869784B1 (ko) * 2002-01-08 2008-11-21 삼성에스디아이 주식회사 생체물질 고정용 발색 화합물 및 이를 이용한 생체물질고정용 코팅막 제조방법
EP2250223A2 (fr) * 2008-02-06 2010-11-17 Barry J. Noar Procede d'incorporation de composes dans des matrices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4656959B2 (ja) * 2004-02-04 2011-03-23 エスケー化研株式会社 床暖房構造体

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2991228A (en) * 1958-03-07 1961-07-04 Lawrence Richard Bruce Inc Composition for bleaching hair
WO1991018007A1 (fr) * 1990-05-15 1991-11-28 Diatron Corporation Phtalocyanatopolyethylene-glycol et saccharides phtalocyanato utilises comme reactifs de digoxine fluorescents
US5246019A (en) * 1989-11-01 1993-09-21 Wella Aktiengesellschaft Process for bleaching hair under the influence of light
WO1995024267A1 (fr) * 1994-03-08 1995-09-14 The Procter & Gamble Company Composition catalytique metallomacrocyclique
US5482514A (en) * 1992-09-14 1996-01-09 Ciba-Geigy Corporation Process for enhancing the whiteness, brightness and chormaticity of paper making fibres
US5484778A (en) * 1990-07-17 1996-01-16 University Hospitals Of Cleveland Phthalocyanine photosensitizers for photodynamic therapy and methods for their use
US5560858A (en) * 1992-07-15 1996-10-01 The Procter & Gamble Company Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer
WO1997005202A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Agents de photoblanchiment faiblement teintes
WO1997005203A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Photodesinfectants faiblement teintes
WO1997010811A1 (fr) * 1995-09-21 1997-03-27 Novartis Ag Nanoparticules utilisees en therapie photodynamique
WO1998032832A1 (fr) * 1997-01-24 1998-07-30 The Procter & Gamble Company Agents de blanchiment a faible teinte
US5846382A (en) * 1992-09-14 1998-12-08 Jorax Gmbh Process for enhancing the whiteness, brightness and chromaticity of fillers and pigments
WO1999014298A1 (fr) * 1997-09-18 1999-03-25 The Procter & Gamble Company Agent de blanchiment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1260829A (zh) * 1997-01-24 2000-07-19 普罗格特-甘布尔公司 含有混合的金属菁的光漂白组合物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2991228A (en) * 1958-03-07 1961-07-04 Lawrence Richard Bruce Inc Composition for bleaching hair
US5246019A (en) * 1989-11-01 1993-09-21 Wella Aktiengesellschaft Process for bleaching hair under the influence of light
WO1991018007A1 (fr) * 1990-05-15 1991-11-28 Diatron Corporation Phtalocyanatopolyethylene-glycol et saccharides phtalocyanato utilises comme reactifs de digoxine fluorescents
US5484778A (en) * 1990-07-17 1996-01-16 University Hospitals Of Cleveland Phthalocyanine photosensitizers for photodynamic therapy and methods for their use
US5484778C1 (en) * 1990-07-17 2001-05-08 Univ Cleveland Hospitals Phthalocynine photosensitizers for photodynamic therapy and methods for their use
US5560858A (en) * 1992-07-15 1996-10-01 The Procter & Gamble Company Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer
US5846382A (en) * 1992-09-14 1998-12-08 Jorax Gmbh Process for enhancing the whiteness, brightness and chromaticity of fillers and pigments
US5482514A (en) * 1992-09-14 1996-01-09 Ciba-Geigy Corporation Process for enhancing the whiteness, brightness and chormaticity of paper making fibres
WO1995024267A1 (fr) * 1994-03-08 1995-09-14 The Procter & Gamble Company Composition catalytique metallomacrocyclique
WO1997005203A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Photodesinfectants faiblement teintes
WO1997005202A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Agents de photoblanchiment faiblement teintes
WO1997010811A1 (fr) * 1995-09-21 1997-03-27 Novartis Ag Nanoparticules utilisees en therapie photodynamique
WO1998032832A1 (fr) * 1997-01-24 1998-07-30 The Procter & Gamble Company Agents de blanchiment a faible teinte
WO1999014298A1 (fr) * 1997-09-18 1999-03-25 The Procter & Gamble Company Agent de blanchiment

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100869784B1 (ko) * 2002-01-08 2008-11-21 삼성에스디아이 주식회사 생체물질 고정용 발색 화합물 및 이를 이용한 생체물질고정용 코팅막 제조방법
EP1588691A1 (fr) * 2004-04-22 2005-10-26 L'oreal Composition pour la déformation permanente des cheveux contenant un réducteur et un photooxydant
FR2869225A1 (fr) * 2004-04-22 2005-10-28 Oreal Composition pour la deformation permanente des cheveux contenant un reducteur et un photooxydant.
EP2250223A2 (fr) * 2008-02-06 2010-11-17 Barry J. Noar Procede d'incorporation de composes dans des matrices
EP2250223A4 (fr) * 2008-02-06 2014-01-15 Barry J Noar Procede d'incorporation de composes dans des matrices

Also Published As

Publication number Publication date
BR0008783A (pt) 2002-04-09
BR9917226A (pt) 2002-02-26
EP1159354A1 (fr) 2001-12-05
MXPA01008952A (es) 2003-07-21
AU3094899A (en) 2000-09-21
AR022825A1 (es) 2002-09-04
MXPA01008987A (es) 2003-07-21
WO2000052122A1 (fr) 2000-09-08
AU4169500A (en) 2000-09-21
EP1159387A1 (fr) 2001-12-05

Similar Documents

Publication Publication Date Title
AU708910B2 (en) Low hue photodisinfectants
US4113857A (en) Process for the preparation of iodophor compounds and methods for stabilizing iodophor pharmaceutical compositions containing the same
CA2304038A1 (fr) Agent de blanchiment
EP0255041B1 (fr) Système de désinfection et de nettoyage de lentilles de contact
EP0851898B1 (fr) Agents de photoblanchiment faiblement teintes
EP0891977B1 (fr) Dérivés de la 5-(4-hydroxyphényl)-porphyrine comme photosensibilisateurs
EP0153278A2 (fr) Composés phtalocyaniniques aquasolubles et leur utilisation comme photoactivateurs
JP2010260874A (ja) 抗菌組成物ならびにその製造および使用方法
EP2265703A1 (fr) Produit détergent ou nettoyant protégeant la couleur
WO2015018700A1 (fr) Composés porphyrinoïdes et appareil pour la photodésinfection de l'eau
NO178226B (no) Blanding inneholdende overflateaktive laktamforbindelser og anvendelser derav
KR100818542B1 (ko) 표면을 살균하거나 소독하는 방법
DE2606519B2 (de) Desinfizierende Zusammensetzung
EP1159354A1 (fr) Composition comprenant un agent photo-oxydant et utilisations de cet agent
US6042744A (en) Bleaching compositions comprising hypochlorite and delivery systems therefor
DE102007058343A1 (de) Verminderung der Adhäsion von Schmutz, Staub und biologischem Material durch Polyesteramide
JP2000159608A (ja) 抗菌性組成物
KR102047144B1 (ko) 히드로겔 형성제를 포함하는 세척 또는 세정 제제
EP0984041B1 (fr) Phtalocyanine métallisée ou non metallisée
JP3472349B2 (ja) 防菌洗浄用組成物
DE102009029370A1 (de) Inhibierung von Körpergerüchen
JPS6157870B2 (fr)
DE19537534A1 (de) Alkylamino-bis-methylensulfon-pyrrolidinium-sulfomethyl-betaine, Verfahren zur Herstellung und ihre Verwendung
DE2033119A1 (de) Waschhilfsmittelzubereitung, die Geweben selbst samtisierende Eigenschaften ver leiht
DD291576A5 (de) Fluessigwaschmittel mit hygienischer wirkung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AT AU AZ BA BB BG BR BY CA CH CN CU CZ CZ DE DE DK DK EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/008952

Country of ref document: MX

Ref document number: 30948/99

Country of ref document: AU

Ref document number: 1999912606

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2001/00834/DE

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 1999912606

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 09936057

Country of ref document: US

WWW Wipo information: withdrawn in national office

Ref document number: 1999912606

Country of ref document: EP