WO2009124855A1 - Use of metal hydrazide complex compounds as oxidation catalysts - Google Patents
Use of metal hydrazide complex compounds as oxidation catalysts Download PDFInfo
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- WO2009124855A1 WO2009124855A1 PCT/EP2009/053722 EP2009053722W WO2009124855A1 WO 2009124855 A1 WO2009124855 A1 WO 2009124855A1 EP 2009053722 W EP2009053722 W EP 2009053722W WO 2009124855 A1 WO2009124855 A1 WO 2009124855A1
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- hydrogen
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- 0 *c1c(*)c(*)*(CN)c(*)c1* Chemical compound *c1c(*)c(*)*(CN)c(*)c1* 0.000 description 8
- OIDIRWZVUWCCCO-UHFFFAOYSA-N CC[n+]1ccccc1 Chemical compound CC[n+]1ccccc1 OIDIRWZVUWCCCO-UHFFFAOYSA-N 0.000 description 1
- OVYMVAQIVITQDP-AWQFTUOYSA-N COc1ccc(/C=N/NC(c2ccc(C(F)(F)F)cc2)=O)c(O)c1 Chemical compound COc1ccc(/C=N/NC(c2ccc(C(F)(F)F)cc2)=O)c(O)c1 OVYMVAQIVITQDP-AWQFTUOYSA-N 0.000 description 1
- YETFAFYLIRLENJ-DJKKODMXSA-N Oc1ccccc1/C=N/NC(c1ccc(C(F)(F)F)cc1)=O Chemical compound Oc1ccccc1/C=N/NC(c1ccc(C(F)(F)F)cc1)=O YETFAFYLIRLENJ-DJKKODMXSA-N 0.000 description 1
Classifications
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- 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
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- 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
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- 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
- A61L12/00—Methods or apparatus for disinfecting or sterilising contact lenses; Accessories therefor
- A61L12/08—Methods or apparatus for disinfecting or sterilising contact lenses; Accessories therefor using chemical substances
- A61L12/12—Non-macromolecular oxygen-containing compounds, e.g. hydrogen peroxide or ozone
- A61L12/124—Hydrogen peroxide; Peroxy compounds
- A61L12/128—Hydrogen peroxide; Peroxy compounds neutralised with catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- 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
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- C11D3/168—Organometallic compounds or orgometallic complexes
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- 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
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- C11D3/32—Amides; Substituted amides
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- 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
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3927—Quarternary ammonium compounds
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
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- 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
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Definitions
- the present invention relates to the use of selected metal complex compounds as oxidation catalysts as well as to a process for removing stains and soil on textiles and hard surfaces.
- the metal complex compounds have hydrazide ligands, preferably with electron withdrawing groups or moieties adjacent to the acyl group. Further aspects of the invention are formulations comprising such metal complex compounds, novel metal complex compounds and novel ligands.
- Metal complex catalysts with hydrazide ligands have in generally been desribed as oxidation catalysts, for example, in DE 196 39 603. However, the compounds disclosed are not active enough. The instant invention solves this problem by introducing electron withdrawing groups in the phenyl ring adjacent to the acyl group.
- the instant metal complex compounds are used especially for enhancing the action of peroxides, for example in the treatment of textile material, without at the same time causing any appreciable damage to fibres and dyeings. There is also no appreciable damage to fibres and dyeings if these metal complexes are used in combination with an enzyme or a mixture of enzymes.
- the instant metal complex compounds may also be used as catalysts for oxidation using molecular oxygen and/or air, that is, without peroxide compounds and/or peroxide-forming substances.
- the bleaching of the fabric can happen during and/or after the treatment of the fibre with the formulation, which comprises the metal complexes.
- Peroxide-containing bleaching agents have long been used in washing and cleaning processes. They have an excellent action at a liquor temperature of 90 0 C and above, but their performance noticeably decreases with lower temperatures.
- Various transition metal ions added in the form of suitable salts, and coordination compounds containing such cations are known to activate H 2 O 2 . In that manner it is possible for the bleaching effect, which is unsatisfactory at lower temperatures, of H 2 O 2 or precursors that release H 2 O 2 and of other peroxo compounds, to be increased.
- the aim of the present invention is accordingly to provide improved metal complex catalysts for oxidation processes that meet the above requirements and, especially, enhance the action of peroxide compounds in the most varied fields of application without causing any5 appreciable damage.
- One aspect of the invention is the use, as a catalyst for oxidation reactions, of at least one complex of formula (1 ) 0 [L n Me m Xp] ⁇ q (1 ),
- Me is manganese, titanium, iron, cobalt, nickel or copper
- X is a coordinating or bridging radical; 5 n is an integer from 1 to 4; m is an integer from 0 to 2; p is an integer having a value of from 0 to 10; z is the charge of the metal complex,
- Y is a counter-ion
- O q z/(charge of Y)
- L is a ligand of formula (2)
- Ri denotes CF 3 or Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cyclo- alkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl which are substituted by one or more electron withdrawing substituents; or phenyl or naphthyl which are substituted by one or more electron withdrawing substituents;
- R 4 denotes hydrogen, CrC 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 - Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl,
- R 2 and R 3 together with the alkylidene carbon atom linking them, form an unsubstituted or substituted 5-, 6-, 7-, 8- or 9-membered ring which may contain further hetero atoms.
- Me represents a metal selected from manganese, titanium, iron, cobalt, nickel or copper, preferably from Mn(II)-(III)-(IV)-(V), Cu(I)-(II)-(III), Fe(I)-(II)-(III)-(IV), Co(I)-(II)-(III), Ni(I)-(II)- (III), Ti(II)-(III)-(IV) and more preferably selected from Mn(II)-(III)-(IV)-(V), Cu(I)-(II)-(III), Fe(I)- (1I)-(III)-(IV) and Co(I)-(II)-(III).
- L represents a ligand as herein defined, or its protonated or deprotonated analogue.
- acyl hydrazone derivatives can be in their E- or Z-configuration.
- the ligand of formula (2) may be in one of its tautomeric forms or as a mixture of its different tautomeric forms.
- Suitable substituents for the alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkinyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl groups are especially Ci-C 4 alkyl; Ci-C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N, N- di-Ci-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N- phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy or naphthyloxy; preferably hydroxyl, halogen and CrC 4 alkoxy.
- Ci-C 4 alkyl Ci-C 4 alkoxy
- hydroxy sulf
- alkyl In general unsubstituted alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkinyl, phenyl, naphthyl, aralkyl, heteroaralkyl and cycloheteroalkyl are preferred.
- Cyclic compounds are preferably 5-, 6- or 7-membered rings, 6-membered rings are preferred.
- Aryl is phenyl or naphthyl.
- the CrCisalkyl radicals mentioned for the compounds of formula (2) are, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
- d-C ⁇ alkyl radicals especially Ci-C 8 alkyl radicals and preferably d-
- alkyl radicals may be unsubstituted or substituted e.g. by hydroxy, Ci-C 4 alkoxy, sulfo or by sulfato, especially by hydroxy.
- the corresponding unsubstituted alkyl radicals are preferred. Very special preference is given to methyl and ethyl, especially methyl.
- aryl radicals that come into consideration for the compounds of formula (2) are phenyl or naphthyl each unsubstituted or substituted by Ci-C 4 alkyl, d-C 4 alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-Ci-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N- naphthylamino, wherein the amino groups may be quaternised, phenyl, phenoxy or by naphthyloxy.
- Preferred substituents are CrC 4 alkyl, Ci-C 4 alkoxy, phenyl and hydroxy.
- Ci-C 6 alkylene groups mentioned for the compounds of formula (2) are, for example, straight-chain or branched alkylene radicals, such as methylene, ethylene, n-propylene or n- butylene. Ci-C 4 alkylene groups are preferred.
- the alkylene radicals mentioned may be unsubstituted or substituted, for example by hydroxy or d-C 4 alkoxy.
- halogen is preferably chlorine, bromine or fluorine, with special preference being given to chlorine.
- C 3 -Ci 2 cycloalkyl refers to saturated cyclic hydrocarbons.
- C 3 -Ci 2 Cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl oder 2-adamantyl.
- C 2 -Ci 8 alkenyl is for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1 ,3- butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1 ,4-pentadien-3-yl, or signifies different isomers of hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
- C3-C 12 cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds such, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen- 1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl or 7,7-dimethyl-2,4-norcaradien-3-yl.
- C 7 -C 9 aralkyl is for example benzyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl.
- C 5 -Ci6heteroaralkyl signifies for example a CrCs alkyl moiety which is substituted with a C 4 -C 8 heteroaryl group, preferably with a C 5 -C 6 heteroraryl group.
- C 5 -C 6 heteroaryl is for example pyridine or pyrimidine.
- X represents any coordinating or bridging species, preferably selected from any mono-, bi- or tri-charged anions and any neutral molecules able to coordinate the metal in a mono-, bi- or tri-dentate manner, preferably selected from O 2 2" , O 2" , RBO 2 2" , RCOO “ , RCONR “ , HOO “ , OH “ , RO “ , NO 3 “ , NO 2 “ , NO, CO, S 2” , RS “ , PO 3 4" , STP-derived anions, PO 3 OR 3” , H 2 O, CO 3 2" , HCO 3 " , ROH, NRR'R", CH 3 CN, RCN, Cl “ , Br “ , OCN “ , SCN “ , CN “ , N 3 “ , F “ , I “ , RO “ , CIO 4 “ , SO 4 2” , HSO 4 -, SO 3 2” , RSO 3 “ , LMeO " and
- Y represents any non-coordinated counter ion, preferably selected from RCOO “ , CIO 4 “ , BF 4 “ , PF 6 “ , RSO 3 “ , RSO 4 “ , SO 4 2” , S 2 O 6 “ , OCN “ , SCN “ , NO 3 “ , NO 2 “ , F “ , Cl “ , Br “ , I “ , RO “ , CIO 4 “ , BR 4 “ , FeCI 4 “ , RBO 2 “ , SO 3 2” , HSO 4 2” , N + RR'R”R'", SbCI 6 “ , CuCI 4 " , CN “ , PO 4 3” , HPO 4 2” , H 2 PO 4 2” , STP- derived anions, CO 3 2” , HCO 3 " , Li + , Ba 2+ , Na + , Mg 2+ , K + , Ca 2+ , Cs + and PR 4 + and more preferably selected from
- R R', R", R' independently represent a group selected from hydrogen, hydroxyl, -ORi 0 wherein R 10 is alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group.
- R, R', R", R' represent hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or Ci -4 -alkyl;
- Y can also be a customary organic counter-ion, for example citrate, oxalate or tartrate.
- Y may be an anion such as RCOO “ , CIO 4 “ , BF 4 “ , PF 6 “ , RSO 3 “ , RSO 4 “ (preferably CF 3 SO 3 “ ), SO 4 2" , OCN “ , SCN “ , NO 3 “ , F “ , Cl “ , Br “ , I “ , RO “ , CIO 4 “ , HSO 4 2” , PO 4 3” , HPO 4 2” , H 2 PO 4 2” , CO 3 2” or HCO 3 " , with R being hydrogen, optionally substituted alkyl or optionally substituted aryl.
- Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation.
- the charge of the counter-ion Y is accordingly preferably 1 +, 2+, 1- or 2-, especially 1 + or 1-. Particularly 1-.
- n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
- m is preferably an integer having a value of 1 or 2, especially 1.
- p is preferably an integer having a value of from O to 4, especially 2.
- z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and especially preferably from 0 to 4+. z is more especially the number 0.
- q is preferably an integer from 0 to 8, especially from 0 to 4, and is especially preferably the number 0.
- X is CH 3 CN, H 2 O, F “ , Cl “ , Br “ , HOO “ , O 2 2” , O 2” , R 28 COO “ , R 28 O “ , LMeO “ and LMeOO “ ;
- Y is R 28 COO “ , CIO 4 “ , BF 4 “ , PF 6 “ , R 28 SO 3 “ , R 28 SO 4 “ , SO 4 2” , NO 3 “ , F “ , Cl “ , Br “ and I “ ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl or phenyl.
- Preferabyl Ri is -(CH 2 ) k -N + (R 1O oR'iooR"ioo)3 A " , wherein A " is an anion and k is a number from 1 to 4; or phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of -0-C(0)ORioo, -COORioo, -C(0)N(Ri 00 R'ioo), -C(O)-Ri 00 , -CN, -NO 2 , -SO 3 Ri 00 , -CF 3 , F, Cl, Br,
- R' 1 00, R"ioo independently are hydrogen, Ci-Ci 8 alkyl or phenyl, or two of Ri 00 , R'i 00 , R"i 00 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; * is the point of attachment and A " is an anion, R 1O i, R'ioi independently are -C(O)-Ri 00 , -C(O)N(Ri 00 R'i 00 ) or -C(O)ORi 00 ; or Ri together with the electron withdrawing substituent is a group
- the anion A " is preferably RCOO “ , CIO 4 “ , BF 4 “ , PF 6 “ , RSO 3 “ , RSO 4 “ (preferably CF 3 SO 3 “ ), SO 4 2" , OCN “ , SCN “ , NO 3 “ , F “ , Cl “ , Br “ , I “ , RO “ , CIO 4 “ , HSO 4 2” , PO 4 3” , HPO 4 2” , H 2 PO 4 2” , CO 3 2” or HCO 3 " , with R being hydrogen, unsubstituted or optionally substituted Ci-Ci 8 alkyl More preferably A " is RSO 3 “ , OCN “ , SCN “ , NO 3 “ , F “ , I “ and Cl “ . Most preferably A “ is Cl “ .
- the catalyst is of formula (3) or (4)
- Me is manganese in oxidation states N-V or iron in oxidation states I to IV;
- X is CH 3 CN, H 2 O, F, Cl “ , Br “ , HOO “ , O 2 2” , O 2" , R 28 COO “ , R 28 O “ ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl or phenyl; p is an integer from 1 to 4;
- Ri is -(CH 2 ) k -N + (R 1O oR'iooR"ioo)3 A " , wherein A " is an anion and k is a number from 1 to 4; or phenyl substituted with 1 to 5 electron withdrawing substituents;
- R 2 denotes hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl,
- R 5 , R 6 , R7 and R 8 independently from each other are hydrogen, unsubstituted or substituted
- Ci-C 28 alkyl C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl,
- the catalyst is of formula (3) or (4) wherein
- Me is manganese in oxidation states H-V or iron in oxidation states I to IV;
- X is CH 3 CN, H 2 O, F, Cl “ , Br “ , HOO “ , O 2 2” , O 2" , R 28 COO “ , R 28 O “ ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl or phenyl; p is an integer from 1 to 4;
- Ri is -(CH 2 ) k -N + (R 1O oR'iooR"ioo)3 A " , wherein A " is an anion and k is a number from 1 to 4; or phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of
- Ri 00 , R'i 00 , R"i 00 are independently hydrogen, Ci-Ci 8 alkyl or phenyl, or two of Ri 00, R'i 00 , R"i 00 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; * is the point of attachment and A " is an anion, Rioi, R'ioi independently are -C(O)-Ri 00 , -C(O)N(Ri 00 R'i 00 ) or -C(O)ORi 00 ; or Ri together with the electron withdrawing substituent is a group
- R 2 denotes hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl, C 5 -Ci 6 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; R 5 , Re, R7 and R 8 independently from each other are hydrogen, unsubstituted or substituted CrC 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9
- R 5 and R 6 , Re and R 7 and/or R 7 and R 8 may be linked together to form 1 , 2 or 3 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more -O-, -S- or - NR 9 - and/or which may be further fused with other aromatic rings and/or which may be substituted with one or more CrC ⁇ alkyl groups.
- Ri in the meaning of phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of -OC(0)ORioo, -COOR100, -C(0)-Rioo, -CN, -NO 2 , -SO 3 RI 00 , -CF 3 , F, Cl, Br, I,
- Ri 00 , R' 1O o, R"ioo are independently hydrogen, d-Ci 8 alkyl or phenyl, or two of Ri 00, R'i 00 , R"i 00 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; * is the point of attachment and A " is an anion, R 1O i, R' 1 0 1 independently are -C(O)-Ri 00 , -C(O)N(Ri 00 R'i 00 ) or -C(O)ORi 00 ; or Ri together with the electron withdrawing substituent is a group
- Ri has the meaning of -(CH 2 ) k -N + (CH 3 ) 3 A " .
- R 5 - R 8 in both phenyl rings can be selected independently from the definitions given above and, for example, R 5 in one ring can have a different meaning from the R 5 in the other ring. This applies equally to the R 6 to R 8 .
- Me is manganese in oxidation states N-V or iron in oxidation states I to IV;
- X is H 2 O, F, Cl “ , Br “ , HOO “ , R 28 COO “ or R 28 O " ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl;
- p is an integer 1 or 2;
- Ri is phenyl substituted with 1 to 5 electron withdrawing substituents selected from the group consisting of
- Ri 00 , R'i 00 , R"i 00 are independently hydrogen, C r Ci 8 alkyl or phenyl, * is the point of attachment and A " is an anion;
- R'ioi independently are -C(O)-Ri 00 , -C(O)N(Ri 00 R'i 00 ) or -C(O)ORi 00 ;
- R 2 , R 5 , Re, R7 and R 8 independently from each other are hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -
- integers m and p in formula (I) are O and the ligand L of formula (2) is used as a catalyst for oxidation reactions;
- the complex compounds of formula (1 ) or the pure ligands of formula (2) are used as catalysts together with peroxide or a peroxide-forming substance, O 2 and/or air for the bleaching of stains or of soiling on textile material in the context of a washing process or by the direct application of a stain remover; for the cleaning of hard surfaces, especially kitchen surfaces, wall tiles or floor tiles; for the use in automatic dishwashing compositions; for the bleaching of stains or of soiling on textile material by atmospheric oxygen, whereby the bleaching is catalysed during and/or after the treatment of the textile in the washing liquor; for the prevention of redeposition of migrating dyes during the washing of textile material; for the use in washing and cleaning solutions having an antibacterial action; as pretreatment agents for bleaching textiles; as catalysts in selective oxidation reactions in the context of organic synthesis; for the waste water treatment; for bleaching in the context of paper-making; for sterilization; and for contact lens disinfection.
- Another aspect of the invention is a process for the bleaching of stains or of soiling on textile materials in the context of a washing process or by the direct application of a stain remover and for the cleaning of hard surfaces comprising bringing into contact a textile material or hard surface material in an aqueous medium, a complex compound of formula (1 ) or a ligand of formula (2) as described above and a peroxide or a peroxide-forming substance or O 2 and/or air.
- the ligands can be prepared according to standard procedures by reacting a carbonyl compound, such as an aldehyde with a primary amine to form the corresponding Schiff base, in particular with a hydrazide of formula (6) with a carbonyl compound of formula (7) wherein the substituents are as defined above.
- the complex (1 ) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (1 ) under conditions of storage or use.
- the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal Me and the ligand L or ligand L-generating species.
- the catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials.
- the active catalyst may be formed in situ in a mixture comprising a salt of the metal Me and the ligand L, or a ligand L- generating species, in a suitable solvent.
- an manganese salt such as MnCI 2 or Mn(OOCCH 3 ) 2 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex.
- the ligand L in another such example, can be mixed with metal Me ions present in the substrate or wash liquor to form the active catalyst in situ.
- Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand L and can be substituted by metal Me ions to form the active complex according to formula (1 ).
- the metal complex compounds of formula (1 ) or the ligands of formula (2) are used together as catalysts with peroxide or a peroxide-forming substance, O 2 and/or air.
- peroxide or a peroxide-forming substance O 2 and/or air.
- Examples that may be mentioned in that regard include the following uses: a) the bleaching of stains or of soiling on textile material in the context of a washing process or by the direct application of a stain remover; b) the cleaning of hard surfaces, especially kitchen surfaces, wall tiles or floor tiles, for example to remove stains that have formed as a result of the action of moulds
- foul stains ("mould stains"); the use in automatic dishwashing compositions is also a preferred use; c) the bleaching of stains or of soiling on textile material by atmospheric oxygen, whereby the bleaching is catalysed during and/or after the treatment of the textile in the washing liquor; d) the prevention of redeposition of migrating dyes during the washing of textile material; e) use in washing and cleaning solutions having an antibacterial action; f) as pretreatment agents for bleaching textiles; g) as catalysts in selective oxidation reactions in the context of organic synthesis; h) waste water treatment; i) use as a catalyst for reactions with peroxy compounds for bleaching in the context of paper-making.
- This relates especially to the delignification of cellulose and bleaching of the pulp, which can be carried out in accordance with customary procedures. Also of interest is the use as a catalyst for reactions with peroxy compounds for the bleaching of waste printed paper; j) sterilisation and k) contact lens disinfection.
- the preferred metals for these uses are manganese and/or iron, in particular manganese.
- metal complex compounds for example, in the bleaching of textile or hard surface material, does not cause any appreciable damage to fibres and dyeings as well as to the hard surface materials, such as table- and kitchen-ware, as well as tiles.
- Processes for bleaching stains in any washing liquor are usually carried out by adding to the washing liquor (with H 2 O 2 or a precursor of H 2 O 2 ) one or more metal complex compounds of formula (1 ).
- a detergent that already comprises one or two metal complex compounds.
- the metal complex compounds of formula (1 ) can alternatively be formed in situ, the metal salt (e.g. manganese(ll) salt, such as manganese(ll) chloride, and/or iron(ll) salt, such as iron(ll) chloride) and the ligand being added in the desired molar ratios.
- a detergent, cleaning, disinfecting or bleaching composition comprising
- V from 0 - 20 wt-%, based on the total weight of the composition, of at least one further additive, and
- such a composition is used for a textile material or a hardsurface material.
- All wt-% are based on the total weight of the detergent, cleaning, disinfecting or bleaching composition.
- the detergent, cleaning, disinfecting or bleaching composition can be any kind of industrial or domestic cleaning, disinfecting or bleaching formulation.
- compositions used for textile material can be used for example in compositions used for textile material as well as in composition used for hardsurfaces, such as hard surface materials, such as table- and kitchen-ware, as well as tiles.
- Preferred hard surface cleaning compositions are dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations.
- the above percentages are in each case percentage by weight, based on the total weight of the composition.
- the compositions preferably contain from 0.005 to 2 wt-% of at least one metal complex compound of formula (1 ), more preferably from 0.01 to 1 wt-% and most preferably from 0.05 to 1 wt-%.
- compositions according to the invention comprise a component A) and/or B)
- the amount thereof is preferably from 1 to 50 wt-%, especially from 1 to 30 wt-%.
- compositions according to the invention comprise a component C
- the amount thereof is preferably from 1 to 70 wt-%, especially from 1 to 50 wt-%. Special preference is given to an amount of from 5 to 50 wt-% and especially an amount of from 10 to 50 wt-%.
- Corresponding washing, cleaning, disinfecting or bleaching processes are usually carried out by using an aqueous liquor containing from 0.1 to 200 mg of one or more compounds of formula (1 ) per litre of liquor.
- the liquor preferably contains from 1 to 50 mg of at least one compound of formula (1 ) per litre of liquor.
- composition according to the invention can be, for example, a peroxide-containing heavy-duty detergent or a separate bleaching additive, or a stain remover that is to be applied directly.
- a bleaching additive is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a bleach-free detergent.
- a bleaching additive can also be used in a liquor together with a bleach-free detergent.
- Stain removers can be applied directly to the textile in question and are used especially for pretreatment in the event of heavy local soiling.
- the stain remover can be applied in liquid form, by a spraying method or in the form of a solid substance, such as a powder especially as a granule.
- Granules can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous suspension comprising all the components listed above except for component E), and then adding the dry component E) and mixing everything together. It is also possible to add component E) to an aqueous suspension containing components A), B), C) and D) and then to carry out spray-drying.
- aqueous suspension that contains components A) and C), but none or only some of component B).
- the suspension is spray-dried, then component E) is mixed with component B) and added, and then component D) is mixed in the dry state. It is also possible to mix all the components together in the dry state.
- the anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzenesulfonat.es, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an ⁇ - sulfonic fatty acid salt or an ester thereof.
- Preferred sulfonates are, for example, alkylbenzenesulfonat.es having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety.
- the average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to
- the cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium.
- Preferred carboxylates are alkali metal sarcosinates of formula R I g-CON(R 2 O)CH 2 COOM 1 wherein R 19 is C 9 -C 17 alkyl or C 9 -C 17 alkenyl, R 20 is CrC 4 alkyl and M 1 is an alkali metal, especially sodium.
- the non-ionic surfactant B) may be, for example, a primary or secondary alcohol ethoxylate, especially a Cs-C 2 O aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C 10 -C 15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group.
- Non-ethoxylated non-ionic surfactants for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.
- the total amount of anionic and non-ionic surfactants is preferably from 5 to 50 wt-%, especially from 5 to 40 wt-% and more especially from 5 to 30 wt-%.
- the lower limit of those surfactants to which even greater preference is given is 10 wt-%.
- the composition may contain cationic surfactants.
- Possible cationic surfactants include all common cationic surface-active compounds, especially surfactants having a textile softening effect. Non-limited examples of cationic surfactants are given in the formulas below:
- each radical R ⁇ is independent of the others C- ⁇ - 6 -alkyl-, -alkenyl- or -hydroxyalkyl; each radical R ⁇ is independent of the others C 8 - 28 -alkyl- or alkenyl; R ⁇ is R ⁇ or (CHz) n -T- R ⁇ ;
- Preferred cationic surfactants present in the composition according to the invention include hydroxyalkyl-trialkyl-ammonium-compounds, especially Ci 2- i 8 -alkyl(hydroxyethyl)dimethyl- ammonium compounds, and especially preferred the corresponding chloride salts.
- Compositions of the present invention can contain between 0.5 wt-% and 15 wt-% of the cationic surfactant, based on the total weight of the compostion.
- alkali metal phosphates especially tripolyphosphates, carbonates and hydrogen carbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.
- Silicates that are especially suitable are sodium salts of crystalline layered silicates of the formula NaHSi t O 2t +i.pH 2 O or Na 2 Si t O 2t+ i.pH 2 O wherein t is a number from 1.9 to 4 and p is a number from O to 20.
- aluminum silicates preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of such components. Special preference is given to zeolite A.
- polycarboxylates preference is given to polyhydroxycarboxylat.es, especially citrates, and acrylates, and also to copolymers thereof with maleic anhydride.
- Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene- diamine disuccinate either in racemic form or in the enantiomerically pure (S, S) form.
- Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof.
- alkali metal salts of 1-hydroxyethane-1 ,1-diphosphonic acid nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof.
- Also preferred polyphosphonates have the following formula
- Ri8 is CH 2 PO 3 H 2 or a water soluble salt thereof and d is an integer of the value O, 1 , 2 or 3.
- polyphosphonates wherein b is an integer of the value of 1.
- the amount of the peroxide or the peroxide-forming substance is preferably 0.5 - 30 wt-%, more preferably 1 - 20 wt-% and especially preferably 1 - 15 wt-%.
- peroxide component D there come into consideration every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.
- inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates.
- Example of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborated monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2- 80 wt-%, preferably from 4-30 wt-%.
- the organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a d-C 4 alkanol oxidase and d-C 4 alkanol (Such as methanol oxidase and ethanol as described in WO95/07972), alkylhydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide.
- the peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
- the bleaching composition of the invention can be suitably formulated to contain from 2 to 80 wt- %, preferably from 4 to 30 wt-%, of the peroxy bleaching agent.
- peroxo acids can also be used.
- M signifies hydrogen or a cation
- R 19 signifies unsubstituted Ci-Ci 8 alkyl; substituted Ci-Ci 8 alkyl; unsubstituted aryl; substituted aryl; -(Ci-C6alkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-C 8 alkylene, wherein the phthalimido and/or the alkylene group may be substituted.
- Preferred mono organic peroxy acids and their salts are those of formula 19 wherein
- M signifies hydrogen or an alkali metal
- R' 19 signifies unsubstituted Ci-C 4 alkyl; phenyl;-CrC 2 alkylene-phenyl or phthalimidoCi-C 8 alkylene.
- CH 3 COOOH and its alkali salts Especially preferred is also ⁇ -phthalimido peroxy hexanoic acid and its alkali salts.
- diperoxyacids for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9- diperoxyazelaic acid, diperoxybrassilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1 ,4-diotic acid and 4,4'-sulphonylbisperoxybenzoic acid.
- DPDA 1,12-diperoxydodecanedioic acid
- 1 DPDA diperoxybrassilic acid
- diperoxysebasic acid diperoxysebasic acid
- diperoxyisophthalic acid diperoxyisophthalic acid
- 2-decyldiperoxybutane-1 ,4-diotic acid 2,4'-sulphonylbisperoxybenzoic acid.
- peroxy acid precursors are the corresponding carboxyacid or the corresponding carboxyanhydrid or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known.
- Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A-0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
- bleach activators include the bleach activators, that carry O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups.
- TAED tetraacetylethylenediamine
- acylated glycolurils especially tetraacetyl glycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium-4-benzoyloxy benzene sulphonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3- benzoloxy benzoate; trimethyl ammonium toluyloxy-benzene sulphonate;acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexa
- R 22 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein
- R 2 i is linear or branched (C 7 -Ci 5 )alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application DE-A-44 43 177. Nitrile compounds that form perimine acids with peroxides also come into consideration as bleach
- peroxyacid bleach precursors are that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751 ,015 and 4,397,757, in EP-A0284292 and EP-A-331 ,229.
- peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC), N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
- SPCC 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride -
- ODC N-octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride -
- a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520, WO 96/40661 and in European Patent Specification No.'s 458,396, 790244 and 464,880.
- These cationic nitriles also known as nitril quats have the formula
- R 30 is a Ci-C 24 alkyl; a Ci-C 24 alkenyl; an alkaryl having a Ci-C 24 alkyl; a substituted d-
- R 31 and R 32 are each independently a Ci-C 3 alkyl; hydroxyalkyl having 1 to 3 carbon atoms, - (C 2 H 4 O) n H, n being 1 to 6; -CH 2 -CN
- R 33 is is a Ci-C 20 alkyl; a Ci-C 20 alkenyl; a substituted Ci-C 20 alkyl; a substituted
- X is an anion
- nitril quats have the following formula
- R 42 and R 43 form, together with the nitrogen atom to which they are bonded, a ring comprising 4 to 6 carbon atoms, this ring may also be substituted by CrC 5 -alkyl,
- Ci-C 5 -alkoxy, Ci-C 5 -alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chloro and 1 or 2 carbon atom(s) of this ring may also be substituted by a nitrogen atom, by a oxygen atom, by a N-R 47 -group and/or by a R 44 -N-R 47 -group, wherein R 47 is hydrogen,
- Ci-C 5 -alkyl C 2 -C 5 -alkenyl, C 2 -C 5 -alkinyl, phenyl, C 7 -C 9 -aralkyl, C 5 -C 7 -cycloalkyl, d-C 5 -alkanoyl, cyanomethyl or cyano,
- R 44 is CrC 24 -, preferably Ci-C 4 -alkyl; C 2 -C 24 - alkenyl, preferably C 2 -C 4 -alkenyl, cyanomethyl or Ci-C 4 -alkoxy-Ci-C 4 -alkyl, R 45 and R 46 are independently from each other hydrogen; Ci-C 4 -alkyl; Ci-C 4 -alkenyl;
- Ci-C 4 -alkoxy-Ci-C 4 -alkyl preferably hydrogen, methyl or phenyl, whereby preferably the moiety R 45 signifies hydrogen, if R 46 is not hydrogen, and
- X " is an anion.
- Suitable examples of nitril quats of formula ( ⁇ ) are
- A is a saturated ring formed by a plurality of atoms in addition to the N 1 atom, the saturated ring atoms to include at least one carbon atom and at least one heteroatom in addition to the N 1 atom, the said one heteroatom selected from the group consisting of O, S and N atoms, the substituent R 47 bound to the N 1 atom of the Formula ( ⁇ ) structure is (a) a OOalkyl or alkoxylated alkyl where the alkoxy is C 2-4 , (b) a C 4 -C 24 cycloalkyl, (c) a C 7 -C 24 alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C 2-4 , or (e) - CR 5 oR5i-C ⁇ N where R 5 o and R 51 are each H, a CrC 24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonre
- the catalyst of formula (1 ) is used together with a peroxide or peroxide precursor and a bleach activator which is selected from the group consisting of tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzene- sulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octanoyl- oxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyl- oxybenzene, undecanoyloxybenzoic acid,
- the precursors may be used in an amount of up to 12 wt-%, preferably from 2-10 wt-% based on the total weight of the composition.
- bleach catalysts which are commonly known, for example transition metal complexes as disclosed in EP 1194514, EP 1383857 or WO04/007657.
- EP832969B1 US6479450B1 , WO9933947A1 , WO0032731A1 , WO03054128A1 , DE102004003710, EP1083730, EP1 148117, EP1445305, US6476996, EP0877078, EP0869171 , EP0783035, EP0761809 and EP1520910.
- compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, ⁇ bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.
- optical brighteners for example from the classes bis-triazinylamino- stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis- benzofuranylbiphenyl, ⁇ bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.
- optical brighteners for example from the classes bis-triazinylamino- stilbene
- Such additives are, for example, dirt-suspending agents, for example sodium carboxymethylcellulose; pH regulators, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and the granulating properties, for example sodium sulfate; perfumes; and also, if appropriate, antistatics and softening agents such as, for example, smectite; bleaching agents; pigments; and/or toning agents. These constituents should especially be stable to any bleaching agent employed. If the detergent composition is used in an automatic dishwasher it is also common to use silver-corrosion inhibitors. Such auxiliaries are added in a total amount of from 0.1 - 20 wt-%, preferably from 0.5 - 10 wt-%, especially from 0.5 - 5 wt-%, based on the total weight of the detergent formulation.
- the detergent may optionally also comprise enzymes.
- Enzymes can be added for the purpose of stain removal.
- the enzymes usually improve the action on stains caused by protein or starch, such as, for example, blood, milk, grass or fruit juices.
- Preferred enzymes are cellulases and proteases, especially proteases.
- Cellulases are enzymes that react with cellulose and its derivatives and hydrolyse them to form glucose, cellobiose and cellooligosaccharides. Cellulases remove dirt and, in addition, have the effect of enhancing the soft handle of the fabric.
- customary enzymes include, but are by no means limited to, the following: proteases as described in US-B-6 242 405, column 14, lines 21 to 32; lipases as described in US-B-6 242 405, column 14, lines 33 to 46; amylases as described in US-B-6 242 405, column 14, lines 47 to 56; and cellulases as described in US-B-6 242 405, column 14, lines 57 to 64.
- Commercially available detergent proteases such as Alcalase ® , Esperase ® , Everlase ® ,
- Savinase ® , Kannase ® and Durazym ® , are sold e.g. by NOVOZYMES A/S.
- detergent amylases such as Termamyl ® , Duramyl ® , Stainzyme ® ,
- Natalase ® , Ban ® and Fungamyl ® are sold e.g. by NOVOZYMES A/S.
- detergent ellulases such as Celluzyme ® , Carezyme ® and Endolase ® , are sold e.g. by NOVOZYMES A/S.
- detergent lipases such as Lipolase ® , Lipolase Ultra ® and Lipoprime ® , are sold e.g. by NOVOZYMES A/S.
- Suitable mannanases such as Mannanaway ® , are sold by NOVOZYMES A/S. Beside in laundry care products, in a hard surface cleaner, especially in a composition used in automatic dishwashers the following enzymes are also commonly used: proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP ® , Optimase ® , Opticlean ® , Maxacal ® , Maxapem ® , Esperase ® and/or Savinase ® , amylases such as Termamyl ® , Amylase-LT ® , Maxamyl ® and/or Duramyl ® , lipases such as Lipolase ® , Lipomax ® , Lumafast ® and/or Lipozym ® .
- proteases such as BLAP ® , Optimase ® , Opticlean ® , Maxacal
- the enzymes which may be used can, as described e.g. in International Patent Applications WO 92/1 1347 and WO 94/23005, be adsorbed on carriers and/or embedded in encapsulating substances in order to safeguard them against premature inactivation. They are present in the cleaning formulations according to the invention preferably in amounts not exceeding 5 wt-%, especially in amounts of from 0.1 wt- % to 1.2 wt-%.
- Amylases The present invention preferably makes use of amylases having improved stability in detergents, especially improved oxidative stability.
- amylases are non-limitingly illustrated by the following: (a) An amylase according to WO 94/02597, Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL ® , or the homologous position variation of a similar parent amylase, such as B.
- amyloliquefaciens B.subtilis, or B.stearothermophilus
- Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha- amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NCIB8061. Any other oxidative stability-enhanced amylase can be used.
- Protease enzymes are usually present in preferred embodiments of the invention at levels between 0.001 wt-% and 5 wt-%.
- the proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used.
- Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Suitable commercial proteolytic enzymes include Alcalase ® , Esperase ® , Durazyme ® , Savinase ® , Maxatase ® , Maxacal ® , and Maxapem ® 15 (protein engineered Maxacal).
- lipases comprise from about 0.001 wt-% to about 0.01 wt-% of the instant compositions and are optionally combined with from about 1 wt-% to about 5 wt-% of a surfactant having limesoap-dispersing properties, such as an alkyldimethylamine N-oxide or a sulfobetaine.
- a surfactant having limesoap-dispersing properties such as an alkyldimethylamine N-oxide or a sulfobetaine.
- Suitable lipases for use herein include those of bacterial, animal and fungal origin, including those from chemically or genetically modified mutants.
- lipases When incorporating lipases into the instant compositions, their stability and effectiveness may in certain instances be enhanced by combining them with small amounts (e.g., less than 0.5 wt-% of the composition) of oily but non-hydrolyzing materials.
- the enzymes when used, may be present in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-% and more especially from 0.1 to 4 wt-%, based on the total weight of the detergent formulation.
- the detergent formulation is a hard surface cleaning composition, preferably a dishwashing detergent formulation, more preferably an automatic dishwashing detergent formulation, then it can optionally also comprises from about 0.001 wt-% to about 10 wt-%, preferably from about 0.005 wt-% to about 8 wt-%, most preferably from about 0.01 wt-% to about 6 wt-% of an enzyme stabilizing system.
- the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
- Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
- compositions may, in addition to comprising the catalysts described herein, also comprise photocatalysts the action of which is based on the generation of singlet oxygen.
- compositions according to the invention are dye-fixing agents and/or polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions.
- polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine-N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000.
- Such polymers are usually used in a total amount of from 0.01 to 5 wt-%, especially from 0.05 to 5 wt-%, more especially from 0.1 to 2 wt-%, based on the total weight of the detergent formulation.
- Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph) and those in WO-A-04/05688.
- inventive detergent composition when used as hardsurface cleaner, especially when the composition is used in automatic dishwasher formulation then, it has been found out, that it is preferable to avoid the use of simple calcium-precipitating soaps as antifoams in the present compositions as they tend to deposit on the dishware. Indeed, phosphate esters are not entirely free of such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the instant compositions.
- foam suppressors are paraffin, paraffin/alcohol combinations, or bisfatty acid amides.
- the hard surface cleaning compositions may also optionally contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP).
- heavy metal chelating agents such as hydroxyethyldiphosphonate (HEDP).
- chelating agents suitable for use herein can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
- Other suitable chelating agents for use herein are the commercial DEQUEST series, and chelants from Nalco, Inc.
- Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprio- nates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldi- glycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
- Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates).
- Further biodegradable sequestrants are, for example, aminoacid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparaginic acid derivatives, such as Baypure CX.
- the aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
- a highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS").
- these chelating agents or transition-metal selective sequestrants will generally comprise from about 0.001 wt-% to about 10 wt-%, more preferably from about 0.05 wt-% to about 1 wt-% of the hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein.
- Preferred hard surface cleaning compositions preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein may additionally contain a dispersant polymer.
- a dispersant polymer is typically at levels in the range from 0 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 20 wt-%, more preferably from about 1 wt-% to about 8 wt-% of the detergent composition.
- Dispersant polymers are useful for improved filming performance of the present dishwasher detergent compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5.
- Particularly preferred are polymers, which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
- Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids.
- the alkali metal, especially sodium salts are most preferred. While the molecular weight of the polymer can vary over a wide range, it preferably is from about 1 ,000 to about 500,000, more preferably is from about 1 ,000 to about 250,000.
- Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
- monomeric segments containing no carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50 wt-% of the dispersant polymer.
- Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50 wt-%, preferably less than about 20 wt-% of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0 wt-% to about 15 wt-%, based on the total weight of the polymer.
- Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
- Such copolymers contain as monomer units: a) from about 90 wt-% to about 10 wt-%, preferably from about 80 wt-% to about 20 wt-% acrylic acid or its salts and b) from about 10 wt-% to about 90 wt-%, preferably from about 20 wt-% to about 80 wt-% of a substituted acrylic monomer or its salt and have the general formula:
- R 3 , Rb, or R c preferably R 3 or R b , is a 1 to 4 carbon alkyl or hydroxyalkyl group; R 3 or R b can be a hydrogen and R c can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R 3 is methyl, R b is hydrogen, and R c is sodium.
- a suitable low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1 ,000 to about 5,000.
- the most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70 wt-% acrylic acid and about 30 wt-% methacrylic acid.
- Other dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000.
- dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
- cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
- Sodium cellulose sulfate is the most preferred polymer of this group.
- Other suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates.
- organic dispersant polymers such as polyaspartate.
- filler materials can also be present in the instant hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations.
- dishwashing detergent formulations preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations.
- these include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70 wt-%, preferably from 0 wt-% to about 40 wt-% of the hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations.
- Preferred filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
- Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates or EDDS in magnesium-salt form. Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein.
- Organic solvents that can be used in the cleaning formulations according to the invention, especially when the latter are in liquid or paste form, include alcohols having from 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having from 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof, and the ethers derivable from the mentioned classes of compound.
- Such water-miscible solvents are present in the cleaning formulations according to the invention preferably in amounts not exceeding 20 wt-%, especially in amounts of from 1 wt-% to 15 wt-%.
- compositions preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils.
- other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered.
- Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.
- Certain hard surface cleaning compositions preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations, comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
- the pH-adjusting components are selected so that when the hard surface cleaning composition, preferably dishwashing detergent formulation, more preferably automatic dishwashing detergent formulation is dissolved in water at a concentration of 1 ,000-5,000 ppm, the pH remains in the range of above about 8, preferably from about 9.5 to about 11.
- the preferred nonphosphate pH-adjusting component can be selected from the group consisting of:
- sodium silicate preferably hydrous sodium silicate having Si ⁇ 2 :Na 2 ⁇ ratio of from about 1 :1 to about 2:1 , and mixtures thereof with limited quantities of sodium metasilicate;
- sodium citrate preferably citric acid;
- sodium bicarbonate preferably borax;
- sodium borate preferably borax;
- sodium hydroxide preferably sodium hydroxide; and
- Preferred embodiments contain low levels of silicate (i.e. from about 3 wt-% to about 10 wt-%
- Illustrative of highly preferred pH-adjusting component systems of this specialized type are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and three- component mixtures of granular sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate.
- the amount of the pH adjusting component in compositions used for automatic dishwashing is preferably from about 1 wt-% to about 50 wt-% of the composition.
- the pH-adjusting component is present in the composition in an amount from about 5 wt-% to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%.
- compositions herein having a pH between about 9.5 and about 1 1 of the initial wash solution particularly preferred automatic dishwashing detergent formulations embodiments comprise, by weight of the automatic dishwashing detergent formulations, from about 5 wt-% to about 40 wt-%, preferably from about 10 wt-% to about 30 wt-%, most preferably from about 15 wt-% to about 20 wt-%, of sodium citrate with from about 5 wt-% to about 30 wt-%, preferably from about 7 wt-% to 25 wt-%, most preferably from about 8 wt-% to about 20 wt- % sodium carbonate.
- the essential pH-adjusting system can be complemented (i.e.
- detergency builder salts selected from nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metals, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties.
- polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
- the detergent formulations can take a variety of physical forms such as, for example, powder granules, tablets (tabs), gel and liquid. Examples thereof include, inter alia, conventional high-performance detergent powders, supercompact high-performance detergent powders and tabs.
- powder granules powder granules, tablets (tabs), gel and liquid.
- examples thereof include, inter alia, conventional high-performance detergent powders, supercompact high-performance detergent powders and tabs.
- One important physical form is the so-called concentrated granular form, which is added to a washing machine.
- compact or supercompact detergents are so-called compact or supercompact detergents.
- Such detergents usually contain only small amounts of fillers or of substances, such as sodium sulfate or sodium chloride, required for detergent manufacture.
- the total amount of such substances is usually from 0 to 10 wt-%, especially from 0 to 5 wt-%, more especially from 0 to 1 wt-%, based on the total weight of the detergent formulation.
- Such (super)compact detergents usually have a bulk density of from 650 to 1000 g/l, especially from 700 to 1000 g/l and more especially from 750 to 1000 g/l.
- the detergent formulations can also be in the form of tablets (tabs).
- tabs The advantages of tabs reside in the ease of dispensing and convenience in handling. Tabs are the most compact form of solid detergent formulation and usually have a volumetric density of, for example, from 0.9 to 1.3 kg/litre. To achieve rapid dissolution, such tabs generally contain special dissolution aids:
- - disintegrators such as cellulose, carboxymethyl cellulose or cross-linked polyvinylpyrrolidone
- the tabs may also comprise combinations of such dissolution aids.
- the detergent formulation may also be in the form of an aqueous liquid containing from 5 wt- % to 50 wt-%, preferably from 10 wt-% to 35 wt-%, of water or in the form of a non-aqueous liquid containing no more than 5 wt-%, preferably from 0 wt-% to 1 wt-% of water.
- Nonaqueous liquid detergent formulations may comprise other solvents as carriers.
- Low molecular weight primary or secondary alcohols for example methanol, ethanol, propanol and isopropanol, are suitable for that purpose.
- the solubilising surfactant used is preferably a monohydroxy alcohol but polyols, such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerol and 1 ,2- propanediol) can also be used.
- Such carriers are usually used in a total amount of from 5 wt- % to 90 wt-%, preferably from 10 wt-% to 50 wt-%, based on the total weight of the detergent formulation.
- the detergent formulations can also used in so-called "unit liquid dose" form.
- an aspect of the invention is a granule comprising a) from 1 - 99 wt-%, based on the total weight of the granule, of at least one metal complex compound of formula (1 ) or a ligand of formula (2) as defined above and of at least one peroxide, b) from 1 - 99 wt-%, based on the total weight of the granule, of at least one binder, c) from 0 - 20 wt-%, based on the total weight of the granule, of at least one encapsulating material, d) from 0 - 20 wt-%, based on the total weight of the granule, of at least one further additive and e) from 0 - 20 wt-% based on the total weight of the granule, of water.
- All wt-% are based on the total weight of the granule.
- binder (b) there come into consideration water-soluble, dispersible or water-emulsifiable anionic dispersants, non-ionic dispersants, polymers and waxes.
- the anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments etc..
- the following products come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenyls or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium
- Especially suitable anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)- alkylnaphthalenesulfonat.es, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.
- Suitable non-ionic dispersants are especially compounds having a melting point of, preferably, at least 35°C that are emulsifiable, dispersible or soluble in water, for example the following compounds:
- fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol
- alkylene oxide especially ethylene oxide, wherein some of the ethylene oxide units may have been replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl phenols, benzyl phenols or alkyl phenols, the alkyl radicals of which have at least 4 carbon atoms;
- alkylene oxide especially propylene oxide, condensation products (block polymers); 4. ethylene oxide/propylene oxide adducts with diamines, especially ethylenediamine;
- sorbitan esters preferably having long-chain ester groups, or ethoxylated sorbitan esters, such as polyoxyethylene sorbitan monolaurate having from 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene oxide units
- addition products of propylene oxide with a tri- to hexa-hydric aliphatic alcohol having from
- fatty alcohol polyglycol mixed ethers especially addition products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol of propylene oxide with aliphatic monoalcohols having from 8 to 22 carbon atoms.
- suitable non-ionic dispersants are surfactants of formula
- R 2 3 is C 8 -C 22 alkyl or C 8 -Ci 8 alkenyl
- R 24 is hydrogen; Ci-C 4 alkyl; a cycloaliphatic radical having at least 6 carbon atoms; or benzyl;
- alkylene is an alkylene radical having from 2 to 4 carbon atoms and n is a number from 1 to 60.
- the substituents R 2 3 and R 24 in formula (11 ) are advantageously each the hydrocarbon radical of an unsaturated or, preferably, saturated aliphatic monoalcohol having from 8 to 22 carbon atoms.
- the hydrocarbon radical may be straight-chain or branched.
- R 23 and R 24 are preferably each independently of the other an alkyl radical having from 9 to 14 carbon atoms.
- Aliphatic saturated monoalcohols that come into consideration include natural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols, e.g.
- Alfols linear primary alcohols having from 8 to 22 carbon atoms.
- Alfols are Alfol (8-10), Alfol (9-1 1 ), Alfol (10-14), Alfol (12-13) and Alfol (16-18).
- Alfol is a registered trade mark of the company Sasol Limited.
- Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.
- the alcohol radicals may be present singly or in the form of mixtures of two or more components, e.g. mixtures of alkyl and/or alkenyl groups that are derived from soybean fatty acids, palm kernel fatty acids or tallow oils.
- Alkylene-O chains are preferably bivalent radicals of the formulae
- cycloaliphatic radical examples include cycloheptyl, cyclooctyl and preferably cyclohexyl.
- non-ionic dispersants there come into consideration preferably surfactants of formula
- R 25 is C 8 -C 22 alkyl
- R 26 is hydrogen or d-C 4 alkyl
- Y 2 , Y3 and Y 4 are each independently of the others hydrogen, methyl or ethyl; n 2 is a number from O to 8; and n 3 is a number from 2 to 40. Further important non-ionic dispersants correspond to formula ⁇ 5 Y 6 Y 7 Y 8
- R 27 is C 9 -Ci 4 alkyl
- R 28 is Ci-C 4 alkyl
- Ys, Y ⁇ , Y7 and Y 8 are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y 5 , Y ⁇ and one of the radicals Y 7 , Y 8 always being hydrogen; and n 4 and n 5 are each independently of the other an integer from 4 to 8.
- non-ionic dispersants of formulae (1 1 ) to (13) can be used in the form of mixtures.
- non-end-group-terminated fatty alcohol ethoxylates of formula (7) e.g. compounds of formula (11 ) wherein R 23 is C 8 -C 22 alkyl, R 24 is hydrogen and the alkylene-0 chain is the radical -(CH 2 -CH 2 -O)- and also end-group-terminated fatty alcohol ethoxylates of formula (9).
- non-ionic dispersants of formulae (11 ), (12) and (13) include reaction products of a Cio-Ci 3 fatty alcohol, e.g.
- Ci 3 oxo-alcohol with from 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide and the reaction product of one mol of a Ci 3 fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, it being possible for the addition products each to be end-group-terminated with Ci-C 4 alkyl, preferably methyl or butyl.
- dispersants can be used singly or in the form of mixtures of two or more dispersants.
- the granules according to the invention may comprise a water-soluble organic polymer as binder.
- Such polymers may be used singly or in the form of mixtures of two or more polymers.
- Water-soluble polymers that come into consideration are, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, polyvinylpyri- dine-N-oxides, copolymers of vinylpyrrolidone with long-chain ⁇ -olefins, copolymers of vinyl- pyrrolidone with vinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinyl- pyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates,
- polyethylene glycols carboxymethyl cellulose
- polyacrylamides polyvinyl alcohols
- polyvinylpyrrolidones gelatin
- hydrolysed polyvinyl acetates copolymers of vinylpyrrolidone and vinyl acetate
- polyacry- lates copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymath- acrylates.
- Suitable water-emulsifiable or water-dispersible binders also include paraffin waxes.
- Encapsulating materials (c) include especially water-soluble and water-dispersible polymers and waxes. Of those materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.
- additives (d) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.
- the preparation of the granules according to the invention is carried out, for example, starting from: a) a solution or suspension with a subsequent drying/shaping step or
- a suspension of the active ingredient in a melt with subsequent shaping and solidification b) a suspension of the active ingredient in a melt with subsequent shaping and solidification.
- a) First of all the anionic or non-ionic dispersant and/or the polymer and, optionally, the further additives are dissolved in water and stirred, if desired with heating, until a homogeneous solution is obtained.
- the catalyst according to the invention is then dissolved or suspended in the resulting aqueous solution.
- the solids content of the solution should preferably be at least 30 wt-%, especially from 40 wt-% to 50 wt-%, based on the total weight of the solution.
- the viscosity of the solution is preferably less than 200 mPas.
- the aqueous solution so prepared, comprising the catalyst according to the invention is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
- a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
- Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous methods and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidised bed granulation processes.
- spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air.
- the atomisation of the solution is effected e.g. using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc.
- the spray-drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidised bed that forms an integral part of the chamber (so-called fluid spray).
- the fine particles ( ⁇ 100 ⁇ m) obtained by a conventional spray-drying process may, if necessary after being separated from the exhaust gas flow, be fed as nuclei, without further treatment, directly into the atomizing cone of the atomiser of the spray-dryer for the purpose of agglomeration with the liquid droplets of the active ingredient.
- the water can rapidly be removed from the solutions comprising the catalyst according to the invention, binder and further additives. It is expressly intended that agglomeration of the droplets forming in the atomising cone, or agglomeration of droplets with solid particles, will take place.
- the catalyst according to the invention is dried in a separate step prior to the melt- granulation and, if necessary, dry-ground in a mill so that all the solids particles are ⁇ 50 ⁇ m in size.
- the drying is carried out in an apparatus customary for the purpose, for example, in a paddle dryer, vacuum cabinet or freeze-dryer.
- product forms of the present invention include product forms specifically developed for industrial and institutional cleaning, for example liquid solutions of the catalyst in water or organic solvents or solid forms such as powders or granules which can be dosed in a separate bleaching step of the cleaning application.
- Ri is -(CH 2 )k-N + (R 1O oR'iooR”ioo)3 A " , wherein A " is an anion and k is a number from 1 to 4; or phenyl substituted with 1 to 5 electron withdrawing substituents -N(R 1O oR'iooR”ioo)3 + A " wherein the
- Rioo, R'-ioo, R"ioo independently are hydrogen, d-Ci 8 alkyl or phenyl, or two of Rioo, R'-ioo, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and
- a " is an anion, or Ri together with the electron withdrawing substituent is a group
- R 4 denotes hydrogen, CrC 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 - Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl, C 5 -Ci 6 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl;
- R 2 and R 3 independently of each other denote hydrogen, unsubstituted or substituted Cr C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 - C 20 heteroalky
- Ri is phenyl substituted with 1 to 5 electron withdrawing substituents -N(R 1O oR'iooR"ioo)3 + A " wherein the
- Rioo, R'-ioo, R"ioo independently are hydrogen, d-Ci 8 alkyl or phenyl, or two of Rioo, R'-ioo, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and A " is an anion, or
- R 4 denotes hydrogen, CrC 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 - Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl, C 5 -Ci 6 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl;
- R 2 and R 3 independently of each other denote hydrogen, unsubstituted or substituted Cr C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 - C 20 heteroalky
- R 2 and R 3 together with the alkylidene carbon atom linking them, form an unsubstituted or substituted ring 5-, 6-, 7-, 8- or 9-membered ring which may contain further hetero atoms.
- Rioo, R'-ioo, R"ioo independently are hydrogen, d-Ci 8 alkyl or phenyl, or two of Rioo, R'-ioo, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and A " is an anion, or
- R 2 denotes hydrogen, unsubstituted or substituted CrC 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl,
- R 5 , R 6 , R 7 and R 8 independently from each other are hydrogen, unsubstituted or substituted
- R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1 , 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more -O-, -S- or - NR 9 - and/or which may be further fused with other aromatic rings and/or which may be substituted with one or more CrC 6 alkyl groups.
- Preferred is a compound wherein Ri is phenyl substituted with 1 to 5 electron withdrawing substituents -N(R 1O oR'iooR"ioo)3 + A " wherein the
- Rioo, R'-ioo, R"ioo independently are hydrogen, Ci-Ci 8 alkyl or phenyl, or two of Rioo, R' I OO, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and A “ is F “ , Cl “ , Br- or I " , or Ri together with the electron withdrawing substituent is a group
- R 2 denotes hydrogen, unsubstituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cyclo- alkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 phenylalkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl halogen;
- R 5 , R 6 , R 7 and R 3 independently from each other are hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl, C 5 -Ci 6 heteroaralkyl; or -ORioo, -NHR 100 , -NR 1oo R'ioo, halogen; or phenyl substituted with 1 to 5 electron withdrawing groups selected from the group consisting of -OC(O)ORi 00 , -COOR100, -C(O)-Ri 00 , -CN, -NO 2 , -SO 3 Ri 00 , -CF 3 , F, Cl,
- Ri is phenyl substituted with 1 to 3 electron withdrawing substituents -N(Ri OO ) 3 + A-, more preferably with 1 or 2 and most preferably with 1.
- Me is manganese in oxidation states H-V or iron in oxidation states I to IV;
- X is CH 3 CN, H 2 O, F, Cl “ , Br “ , HOO “ , O 2 2” , O 2" , R 28 COO “ , R 28 O “ ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl or phenyl; p is an integer from 1 to 4;
- Ri is -(CH 2 ) k -N + (R 1O oR'iooR”ioo)3 A " , wherein A " is an anion and k is a number from 1 to 4; or phenyl substituted with 1 to 5 electron withdrawing substituents -N(R 1O oR'iooR”ioo)3 + A " wherein the
- Rioo, R'-ioo, R"ioo independently are hydrogen, Ci-Ci 8 alkyl or phenyl, or two of Rioo, R'ioo, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and A “ is F “ , Cl “ , Br “ or I, or
- R 2 denotes hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl,
- R 5 , R 6 , R7 and R 8 independently from each other are hydrogen, unsubstituted or substituted
- Ci-C 28 alkyl C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl,
- R 5 and R 6 , Re and R 7 or R 7 and R 8 are linked together to form 1 , 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more -O-, -S- or -
- Me is manganese in oxidation states N-V or iron in oxidation states I to IV;
- X is CH 3 CN, H 2 O, F, Cl “ , Br “ , HOO “ , O 2 2” , O 2" , R 28 COO “ , R 28 O “ ;
- R 28 is hydrogen, unsubstituted or substituted Ci-Ci 8 alkyl or phenyl; p is an integer from 1 to 4;
- Ri is phenyl substituted with 1 to 5 electron withdrawing substituents -N(R 1O oR'iooR"ioo)3 + A " wherein the
- Rioo, R'100, R"ioo independently are hydrogen, Ci-Ci 8 alkyl or phenyl, or two of Rioo, R'100, R"ioo together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further nitrogen atom; and A “ is F “ , Cl “ , Br “ or I, or
- R 2 denotes hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -Ci 2 cycloheteroalkyl, C 5 -Ci 6 heteroaralkyl, unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl; R 5 , R 6 , R7 and R 8 independently from each other are hydrogen, unsubstituted or substituted Ci-C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl, C 7 -C 9
- R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are linked together to form 1 , 2, 3 or 4 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more -O-, -S- or -
- E/Z isomers and tautomeric forms 1.39 g of 3-nitrobenzhydrazide are stirred for 30 min. in 35 mL of ethanol. Then 0.93 g of salicyl aldehyde are added dropwise at room temperature. After addition of 1 mL of concentrated hydrochloric acid a yellow suspension is formed. The yellow suspension is stirred for 16 hours at room temperature. The precipitate is then filtrated off, washed with 10 mL of water and dried in the vacuum at 100 0 C yielding 2.00 g of the desired product as a yellowish powder. Melting point: 243.7°C.
- the bleaching action of the compounds according to the invention is by far superior to the reference of 10 mM hydrogen peroxide alone.
- the increase in the lightness DY difference in lightness according to CIE
- the increase in the lightness DY difference in lightness according to CIE
- a value >0 indicates catalytic activity.
- the manganese complexes exhibit a very good bleaching action.
- the increase in the lightness DY (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically.
- the Ligand L10 exhibits a very good bleaching action, even on top of a SPC/TAED bleach system.
- the ligand L9 exhibits a very good bleaching action, which exceeds the performance of the standard bleach system SPC/TAED.
- un-complexed ligand (bleach activity with liquid bleach additive) 48 g of white cotton fabric and 0.8 g of BC01 tea-stained and 0.8g EMPA114 red wine or 0.8g BC03 tea and BC06 strawberry-stained cotton fabric are treated in 250 ml of washing liquor.
- the liquor contains a commercial color care washing powder in a concentration of 4.5g/l, 2.4g/l of a commercial liquid bleach additive (Vanish).
- the catalyst concentration Ligand L10 in a un-complexed form is 10 ⁇ mol/l and 20 ⁇ mol/l.
- the washing process is carried out in a steel beaker in a LINITEST apparatus for 40 minutes at 40 0 C.
- the increase in the lightness DY difference in lightness according to CIE
- the higher the ⁇ Y value the better the bleach performance.
- the ligand L10 exhibits a very good bleaching action also with liquid bleach additives.
- the washing process is carried out in a steel beaker in a LINITEST apparatus for 40 minutes at 40 0 C.
- the increase in the lightness DY difference in lightness according to CIE
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Abstract
Description
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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EP18206014.5A EP3524347A1 (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts |
ES09731048T ES2727511T3 (en) | 2008-04-09 | 2009-03-30 | Use of hydrazide compounds as oxidation catalysts |
PL09731048T PL2271426T3 (en) | 2008-04-09 | 2009-03-30 | Use of hydrazide compounds as oxidation catalysts |
BRPI0909022-3A BRPI0909022B1 (en) | 2008-04-09 | 2009-03-30 | use of at least one compound, detergent, cleaner, disinfectant or bleach composition, and granule |
CN2009801126714A CN101990464B (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts |
JP2011503401A JP5795254B2 (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts |
EP09731048.6A EP2271426B1 (en) | 2008-04-09 | 2009-03-30 | Use of hydrazide compounds as oxidation catalysts |
MX2010010961A MX2010010961A (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts. |
US12/936,699 US8492324B2 (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts |
AU2009235571A AU2009235571B2 (en) | 2008-04-09 | 2009-03-30 | Use of metal hydrazide complex compounds as oxidation catalysts |
US13/920,381 US8791298B2 (en) | 2008-04-09 | 2013-06-18 | Use of metal hydrazide complex compounds as oxidation catalysts |
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US13/920,381 Division US8791298B2 (en) | 2008-04-09 | 2013-06-18 | Use of metal hydrazide complex compounds as oxidation catalysts |
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EP (2) | EP3524347A1 (en) |
JP (1) | JP5795254B2 (en) |
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CN (1) | CN101990464B (en) |
AU (1) | AU2009235571B2 (en) |
BR (1) | BRPI0909022B1 (en) |
ES (1) | ES2727511T3 (en) |
MX (1) | MX2010010961A (en) |
PL (1) | PL2271426T3 (en) |
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Also Published As
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EP2271426B1 (en) | 2019-02-20 |
TR201905689T4 (en) | 2019-05-21 |
ES2727511T3 (en) | 2019-10-16 |
BRPI0909022B1 (en) | 2020-11-10 |
EP3524347A1 (en) | 2019-08-14 |
AU2009235571A1 (en) | 2009-10-15 |
CN101990464B (en) | 2013-10-23 |
KR20100134102A (en) | 2010-12-22 |
US8791298B2 (en) | 2014-07-29 |
JP5795254B2 (en) | 2015-10-14 |
MX2010010961A (en) | 2010-11-05 |
US20110071066A1 (en) | 2011-03-24 |
US8492324B2 (en) | 2013-07-23 |
AU2009235571B2 (en) | 2013-12-19 |
BRPI0909022A2 (en) | 2019-10-01 |
EP2271426A1 (en) | 2011-01-12 |
JP2011516253A (en) | 2011-05-26 |
CN101990464A (en) | 2011-03-23 |
KR101591543B1 (en) | 2016-02-03 |
US20130281353A1 (en) | 2013-10-24 |
PL2271426T3 (en) | 2019-08-30 |
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