EP0553608B1 - Detergent compositions inhibiting dye transfer in washing - Google Patents
Detergent compositions inhibiting dye transfer in washing Download PDFInfo
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- EP0553608B1 EP0553608B1 EP19920870019 EP92870019A EP0553608B1 EP 0553608 B1 EP0553608 B1 EP 0553608B1 EP 19920870019 EP19920870019 EP 19920870019 EP 92870019 A EP92870019 A EP 92870019A EP 0553608 B1 EP0553608 B1 EP 0553608B1
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- Prior art keywords
- dye transfer
- composition according
- metallo
- transfer inhibiting
- inhibiting composition
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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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
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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
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
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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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof
Definitions
- the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
- GB-A-2 101 167 describes a stable liquid bleaching composition containing a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dilution.
- U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphins. Transfer of a textile dye can be inhibited by adding an enzyme exhibiting peroxidase or oxidase activity to the wash liquor in which fabrics are washed and/or rinsed, as described in WO-A-91/05839.
- EP-A-0 537 381 relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydrogen peroxide and porphin catalysts.
- EP-A-0 369 678 relates to the improvement of the bleaching properties of bleaching compositions comprising C1-C4 alkanol oxidase and a C1-C4 alkanol by the addition of a C1-C4 aldehyde oxidase having a lower Km than the C1-C4 alkanol oxidase.
- EP-A-0 308 101 discloses the catalytic preparation of tertiary butyl alcohol wherein the catalyst is selected from (a) a metal porphine compound; (b) a soluble ruthenium catalyst promoted with a bidentate ligant; and (c) a promoted metal phthalocyanine compound.
- the catalyst is selected from (a) a metal porphine compound; (b) a soluble ruthenium catalyst promoted with a bidentate ligant; and (c) a promoted metal phthalocyanine compound.
- the reaction yield and selectivity is improved if the catalyst composition also contains an appropriate mercaptan and/or an appropriate amine.
- the addition of said catalyst stabilizers reduces the rate of self-destruction of the porphin catalyst resulting in improved through-the-wash stability of the porphin catalyst.
- said catalyst stabilizers accelerate the oxidation reactivity of the porphin catalyst thereby increasing the rate of the dye bleaching.
- a dye transfer inhibiting composition which exhibits optimum dye transfer inhibiting properties.
- the invention provides an efficient process for laundering operations involving colored fabrics.
- the present invention relates to inhibiting dye transfer compositions comprising :
- a process is also provided for laundering operations involving colored fabrics.
- the present invention provides a dye transfer inhibiting composition comprising :
- the oxidizing agent, hydrogen peroxide is generated in situ by using an enzymatic hydrogen peroxide generation system.
- the use of an enzymatic hydrogen peroxide generating system allows the continuous generation of low levels of hydrogen peroxide and provides a practical way of controlling a low steady-state level of hydrogen peroxide. Maximum effectiveness occurs when the component levels are such that the hydrogen peroxide is replenished at a rate similar to its removal due to the oxidation of dyes in the wash water.
- the enzyme used in the present invention is an oxidase.
- the oxidase is present by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition. One unit is the amount of enzyme needed to convert 1 ⁇ mole of substrate per minute.
- Suitable oxidases are urate oxidase, galactose oxidase, alcohol oxidases, amine oxidases, amino acid oxidases, cholesterol oxidase and glucose oxidase, malate oxidase, glycollate oxidase, hexose oxidase, aryl alcohol oxidase, L-gulonolactose oxidase, pyranose oxidase, L-sorbose oxidase, pyridoxine 4-oxidase, 2-2-hydroxyacid oxidase, choline oxidase, ecdysone oxidase.
- the preferred enzymatic systems are alcohol and aldehyde oxidases, glucose oxidase.
- the more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glucose oxidase to glucoronic acid with the formation of hydrogen peroxide.
- solid alcohols e.g. glucose whose oxidation is catalysed by glucose oxidase to glucoronic acid with the formation of hydrogen peroxide.
- liquid alcohols which could for example, also act as solvents.
- An example is ethanol/ethanol oxidase.
- the quantity of oxidase to be employed in compositions according to the invention should be at least sufficient to provide in the wash a constant generation of 0.005 to 10 ppm AvO per minute.
- this can be achieved at room temperature and at pH 6 to 11, preferentially 7 to 9 with 1-20000 U/l glucose oxidase, 0.005 to 0.5 % glucose under constant aeration in the washing process.
- the preferred usage range of the catalyst in the wash is 10 -8 molar to 10 -3 molar, more preferred 10 -6 - 10 -4 molar.
- the essential metallo porphin structure may be visualized as indicated in Formula I in the accompanying drawings.
- Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been omitted in the drawings, but are actually present as in I.
- Preferred metallo porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso positions), with a phenyl or pyridyl substituent selected from the group consisting of wherein n and m may be 0 or 1; A may be sulfate, sulfonate, phosphate or carboxylate groups; and B is C 1 -C 10 alkyl, polyethoxy alkyl or hydroxy alkyl.
- Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of -CH 3 , -C 2 H 5 , -CH 2 CH 2 CH 2 SO 3 - , -CH 2 COO - , and -CH 2 CH(OH)CH 2 SO 3 - , SO 3 - .
- a particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10 15, and 20 carbon positions with the substituent
- This preferred compound is known as metallo tetrasulfonated tetraphenylporphin.
- the symbol X 2 of Formula I represents an anion, preferably OH - or Cl - .
- the compound of Formula I may be substituted at one or more of the remaining carbon positions with C 1 -C 10 alkyl, hydroxyalkyl or oxyalkyl groups.
- Porphin derivatives also include chlorophyls, chlorines, i.e. isobacterio chlorines and bacteriochlorines.
- Metallo porphyrin and water-soluble or water-dispersable derivatives thereof have a structure given in formula II.
- X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate, aryl.
- X 2 of Formula II represents an anion, preferably OH - or Cl - .
- the symbol X i can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate.
- Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally.
- the anionic groups in the above structures contain cations selected from the group consisting of sodium and potassium cations or other non-interfering cations which leave the structures water-soluble.
- Preferred phthalocyanine derivatives are metallo phthalocyanine trisulfonate and metallo phthalocyanine tetrasulfonate.
- substitution of the central metal is substitution of the central metal by Fe, Mn, Co Rh, Cr, Ru, Mo or other transition metals.
- the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compound for the surface.
- strongly negatively charged substituted compounds for instance the tetrasulfonated porphin, may be repelled by negatively charged stains or stained surfaces and are therefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be attracted to, or at least not repelled by such stained surfaces.
- the dye transfer inhibiting benefits can be optimized by adding small amounts of catalyst stabilizers.
- catalyst e.g. metallo porphins are susceptible to self-destruction.
- the level of catalyst should be such that sufficient active catalyst is present to bleach the dyes throughout the total wash cycle.
- the stability of metallo catalyst used in the present invention is improved by adding amine base catalyst stabilizers capable of binding the 5th ligand of the central atom in the metallo porphin structure.
- Preferred heterocyclic compounds suitable for the present invention are imidazole compounds of the formula : wherein Y is hydrogen or oxygen or a C 1 -C 12 alkyl, R i , R 1 and R 2 are selected independently hydrogen or C 1 -C 30 alkyl or alkenyl groups, and X is selected from the group of : ⁇ R 3 ⁇ ⁇ R 3 ⁇ O ⁇ wherein R 3 is a C 1 -C 5 alkanediyl group, or is with n being an integer from 0 to 10, and m is an integer from 0 to 2, n+m>1, and R 4 being a C 1-4 alkyl group or hydrogen.
- imidazole derivatives including histidine, purines, hipoxanthine, imidazolidicarboxylic acid, histamine, polyhistidine, alkylated imidazole.
- heterocyclic compounds suitable for the present invention are pyridine and alkylated pyridines and derivatives thereof, pyrole and derivatives thereof.
- Non heterocyclic compounds capable of binding the 5th ligand of the central atom in the porphin structure are suitable for the present invention.
- non heterocyclic compounds include non heterocyclic amines, having the formula (C 2 H 5 ) 3 N, C 3 H 7 NH 2 , (C 6 H 11 ) 2 NH, 1,5 - diazabicyclo[4.3.0]non-5-ene.
- the catalyst stabilizers of the present invention reduce the deposition of the porphin catalyst onto the fabric, resulting in better whiteness maintenance of white fabrics. Also, it has been found that the addition of the catalyst stabilizers mentioned hereinabove not only results in less self-destruction of the structure but also results in less deposition of oxidized or non oxidized porphin.
- the rate of dye oxidation by the porphin catalyst is greatly enhanced by the presence of the said catalyst stabilizers. This results in an increased dye bleaching.
- the amine base catalyst stabilizer is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.
- the present compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations.
- the present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.
- a wide range of surfactants can be used in the detergent compositions.
- anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
- Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source preferably from a C 16 -C 18 fatty source.
- the cation is an alkali metal, preferably sodium.
- Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
- alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C 14-15 alkyl sulphates.
- the cation in each instance is again an alkali metal cation, preferably sodium.
- One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
- HLB hydrophilic-lipophilic balance
- the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
- Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
- Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
- nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
- R 1 is methyl
- R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
- Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
- compositions according to the present invention may further comprise a builder system.
- a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
- phosphate builders can also be used herein.
- Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
- Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst).
- SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 5 ).
- Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
- Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate.
- Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
- Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US-A-4,663,071.
- suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps.
- Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
- the preferred unsaturated fatty acid is oleic acid.
- Another preferred builder system for liquid compositions is based on dodecenyl succinic acid.
- Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
- Other builder materials that can form part of the builder system for use in granular compositions for the purposes of this invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
- Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
- Polymers of this type are disclosed in GB-A-1,596,756.
- Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
- Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
- compositions of the present invention should be free from conventional bleaching agents.
- Other components used in detergent compositions may be employed, such as suds boosting or depressing agents, enzymes and stabilizers or activators therefore, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
- soil-suspending agents soil-release agents such as soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
- enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/rejuvenation.
- These components, particularly the enzymes, optical brighteners, coloring agents, and perfumes should preferably be chosen such that they are compatible with the bleach component of the composition.
- the detergent compositions according to the invention can be in liquid, paste or granular forms.
- Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
- the present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
- the process comprises contacting fabrics with a laundering solution as hereinbefore described.
- the process of the invention is conveniently carried out in the course of the washing process.
- the washing process is preferably carried out at 5°C to 90°C, especially 20 to 60, but the catalysts are effective at up to 95°C.
- the pH of the treatment solution is preferably from 7 to 11, especially from 7.0 to 9.0.
- the process and compositions of the invention can also be used as additive during laundry operations.
- composition A A detergent solution (100mL) containing dyes (40 ppm final concentration), glucose (0.1% by weight) and a ferric tetrasulfonated tetraphenylporphin catalyst (1 x 10 -5 M) was prepared and its pH value adjusted to 8.0.
- Composition B A detergent solution (100mL) containing dyes (40 ppm final concentration), glucose (0.1% by weight), and ferric tetrasulfonated tetraphenylporphin catalyst (2.5 x 10 -6 M) and imidazole (10 mM) was prepared and its pH value adjusted to pH 8.0.
- the absorbance spectrum was recorded (350-750 nm). This region encompasses the wavelength maximum of the dyes (as noted in the table below) and the Soret band of the catalyst (414 nm). Glucose oxidase (final concentration 0.1U/mL) was then added to the stirred solution to initiate the reaction. After 30 min the absorbance spectrum was recorded and the decrease in the absorbance maximum of the dyes noted. Blank experiments indicated that no oxidation of the dyes occurred over the same period in the absence of catalyst or glucose oxidase.
- a detergent solution (100mL) of glucose (0.1% by weight) and different metallo catalysts (10 x 10 -5 M) was prepared and the pH adjusted to 8.0. To initiate the reaction, different levels of glucose oxidase were added. The destruction of the catalyst was measured in each case by quantifying the decrease in absorption of the Soret band (414 nm). The catalyst destruction was compared with and without imidazole at different time intervals.
- FeTPPS ferric tetrasulfonated tetraphenylporphin catalyst
- a liquid dye transfer inhibiting composition according to the present invention is prepared, having the following compositions : % Linear alkylbenzene sulfonate 10 Alkyl sulphate 4 Fatty alcohol (C 12 -C 15 ) ethoxylate 12 Fatty acid 10 Oleic acid 4 Citric acid 1 NaOH 3.4 Propanediol 1.5 Ethanol 5 Ethanoloxidase 5 u/ml Ferric tetrasulfonated tetraphenylporphin 0.1 imidazole 3 Minors up to 100
- a compact granular dye transfer inhibiting composition according to the present invention is prepared, having the following formulation: % Linear alkyl benzene sulphonate 11.40 Tallow alkyl sulphate 1.80 C 45 alkyl sulphate 3.00 C 45 alcohol 7 times ethoxylated 4.00 Tallow alcohol 11 times ethoxylated 1.80 Dispersant 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Citric acid 3.00 Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 DETMPA 1.00 Cellulase (active protein) 0.03 Alkalase/BAN 0.60 Lipase 0.36 Sodium silicate 2.00 Sodium sulphate 3.50 Ferric tetrasulfonated tetraphenylporphin 0.025 Glucose 10.00 Glucose oxidase 100 u/ml imidazole 3 Minors up to 100
Description
The enzyme used in the present invention is an oxidase.
The oxidase is present by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition. One unit is the amount of enzyme needed to convert 1 µmole of substrate per minute.
-CH3, -C2H5, -CH2CH2CH2SO3 -, -CH2COO-, and -CH2CH(OH)CH2SO3 -, SO3 -.
It is well known in art that catalyst e.g. metallo porphins are susceptible to self-destruction. As a result of said selfdestruction, the level of catalyst should be such that sufficient active catalyst is present to bleach the dyes throughout the total wash cycle.
It has now been found that the stability of metallo catalyst used in the present invention is improved by adding amine base catalyst stabilizers capable of binding the 5th ligand of the central atom in the metallo porphin structure. Preferred heterocyclic compounds suitable for the present invention are imidazole compounds of the formula : wherein Y is hydrogen or oxygen or a C1-C12 alkyl, Ri, R1 and R2 are selected independently hydrogen or C1-C30 alkyl or alkenyl groups, and X is selected from the group of :
Second, the catalyst stabilizers of the present invention reduce the deposition of the porphin catalyst onto the fabric, resulting in better whiteness maintenance of white fabrics.
Also, it has been found that the addition of the catalyst stabilizers mentioned hereinabove not only results in less self-destruction of the structure but also results in less deposition of oxidized or non oxidized porphin.
The amine base catalyst stabilizer is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.
The present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5).
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US-A-4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid.
Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
Other builder materials that can form part of the builder system for use in granular compositions for the purposes of this invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
These components, particularly the enzymes, optical brighteners, coloring agents, and perfumes, should preferably be chosen such that they are compatible with the bleach component of the composition.
Composition A: A detergent solution (100mL) containing dyes (40 ppm final concentration), glucose (0.1% by weight) and a ferric tetrasulfonated tetraphenylporphin catalyst (1 x 10-5 M) was prepared and its pH value adjusted to 8.0.
Composition B: A detergent solution (100mL) containing dyes (40 ppm final concentration), glucose (0.1% by weight), and ferric tetrasulfonated tetraphenylporphin catalyst (2.5 x 10-6 M) and imidazole (10 mM) was prepared and its pH value adjusted to pH 8.0.
Glucose oxidase (final concentration 0.1U/mL) was then added to the stirred solution to initiate the reaction. After 30 min the absorbance spectrum was recorded and the decrease in the absorbance maximum of the dyes noted.
Blank experiments indicated that no oxidation of the dyes occurred over the same period in the absence of catalyst or glucose oxidase.
% destruction of dye | ||||
Dyes | CI # | lmax | COMP A | COMP B |
Acid Blue 9 | 42000 | 630 nm | 13 | 53 |
Direct blue 98 | 23155 | 570 nm | 62 | 90 |
Direct blue 120 | 34090 | 570 nm | 50 | 83 |
Acid blue 113 | 26360 | 595 nm | 39 | 95 |
FD&C Red 40 | 16035 | 500 nm | 0 | 30 |
Acid Yellow 40 | 18950 | 440 nm | 0 | 30 |
Conclusion : Even though a lower level of iron porphin catalyst is present in composition B, dyes are oxidized to a much bigger extent compared to composition A containing 4 times the iron porphin catalyst level. |
The catalyst destruction was compared with and without imidazole at different time intervals.
% catalyst destruction | ||||||
U Glox/ mL | No imidazole | With 10 mM imidazole | ||||
10 min | 20 min | 30 min | 10 min | 20 min | 30 min | |
Iron Tetrasulfonated tetraphenylporphin | ||||||
0.1 | 53 | 7 | 0 | 92 | 87 | 82 |
Hemin chloride | ||||||
0.05 | 67 | 42 | 29 | 100 | 93 | 89 |
0.25 | 33 | 21 | 13 | 92 | 68 | 49 |
Iron phthalocyanine tetrasulfonated | ||||||
0.05 | 69 | 31 | 18 | 88 | 85 | 82 |
0.1 | 47 | 16 | 0 | 88 | 83 | 80 |
Mangano phthalocyanine tetrasulfonated | ||||||
0.1 | 30 | 0 | 0 | 77 | 69 | 62 |
This experimental procedure was repeated with and without imidazole (10 mM).
solution | % Porphyrin left in solution |
FeTPPS only | 50 |
FeTPPS+Imidazole | 84 |
Conclusion : The presence of imidazole strongly reduces the tendency of FeTPPS to deposit onto fabrics. |
% | |
Linear alkylbenzene sulfonate | 10 |
Alkyl sulphate | 4 |
Fatty alcohol (C12-C15) ethoxylate | 12 |
Fatty acid | 10 |
Oleic acid | 4 |
Citric acid | 1 |
NaOH | 3.4 |
Propanediol | 1.5 |
Ethanol | 5 |
Ethanoloxidase | 5 u/ml |
Ferric tetrasulfonated tetraphenylporphin | 0.1 |
imidazole | 3 |
Minors | up to 100 |
% | |
Linear alkyl benzene sulphonate | 11.40 |
Tallow alkyl sulphate | 1.80 |
C45 alkyl sulphate | 3.00 |
C45 alcohol 7 times ethoxylated | 4.00 |
Tallow alcohol 11 times ethoxylated | 1.80 |
Dispersant | 0.07 |
Silicone fluid | 0.80 |
Trisodium citrate | 14.00 |
Citric acid | 3.00 |
Zeolite | 32.50 |
Maleic acid actylic acid copolymer | 5.00 |
DETMPA | 1.00 |
Cellulase (active protein) | 0.03 |
Alkalase/BAN | 0.60 |
Lipase | 0.36 |
Sodium silicate | 2.00 |
Sodium sulphate | 3.50 |
Ferric tetrasulfonated tetraphenylporphin | 0.025 |
Glucose | 10.00 |
Glucose oxidase | 100 u/ml |
imidazole | 3 |
Minors | up to 100 |
Claims (22)
- A dye transfer inhibiting composition comprising:
a metallo catalyst selected froma) metallo porphin and water-soluble or water-dispersable derivatives thereof;b) metallo porphyrin and water-soluble or water-dispersable derivatives thereof;c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof; - A dye transfer inhibiting compositions according to claim 1 wherein said amine base catalyst stabilizer is selected from imidazole and derivates thereof.
- A dye transfer inhibiting composition according to claim 1 wherein said amine base catalyst stabilizer is selected from pyridine and its derivatives thereof.
- A dye transfer inhibiting composition according to claim 1-3 wherein said enzymatic system comprises an oxidase and as a substrate an alcohol, an aldehyde or a combination of both.
- A dye transfer inhibiting composition according to claim 1-4, containing a metallo porphin derivative, wherein said iron porphin is substituted on at least one of its meso positions with a phenyl or pyridyl substituent selected from the group consisting of wherein n and m may be 0 or 1, A is selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate groups, and B is selected from the group consisting of C1-C10 alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.
- A dye transfer inhibiting composition according to claim 5 wherein the substituents on the phenyl or pyridyl groups are selected from the group consisting of -CH3, -C2H5, -CH2CH2CH2SO3 -, -CH2COO-, -CH2CH(OH)CH2SO3 -, and -SO3 -.
- A dye transfer inhibiting composition according to claims 1-4, containing a metallo porphin derivative, wherein said metallo porphin is substituted on at least one of its meso positions with a phenyl substituent selected from the group consisting of wherein X1 is (=CY-) wherein each Y, independently, is hydrogen, chlorine, bromine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.
- A dye transfer inhibiting composition according to claim 7 wherein the catalyst compound is metallo tetrasulfonated tetraphenylporphin.
- A dye transfer inhibiting composition according to claim 1 wherein the metallo of said metallo catalyst is substituted by Fe, Mn, Co, or other transition metals.
- A dye transfer inhibiting composition according to claim 1 wherein the concentration of metallo catalyst is from 10-8 to 10-3 molar, preferably from 10-6 to 10-4 molar.
- A dye transfer inhibiting composition according to claim 4 wherein the oxidase is present by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition.
- A dye transfer inhibiting composition according to claim 4 wherein said substrate is glucose.
- A dye transfer inhibiting composition according to claim 4 wherein said substrate consists of a C1-C6 alcohol.
- A dye transfer inhibiting composition according to claim 10 wherein said substrate is ethanol.
- A dye transfer inhibiting composition according to claim 3 in which the substrate is present from 0.1 to 50% by weight of the composition.
- A dye transfer inhibiting composition according to claim 1 which yields hydrogen peroxide at a concentration from 0.005 to 10 ppm/min in the wash process.
- A dye transfer inhibiting composition according to claim 1 wherein said catalyst stabilizer is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.
- A dye transfer inhibiting composition according to claims 1-17 which is a detergent additive, in the form of a non-dusting granule or a liquid.
- A process for inhibiting dye transfer between fabrics during laundering operations involving colored fabrics, said process comprising contacting said fabrics with a laundering solution containing a dye transfer inhibition composition according to claims 1-18.
- A process for inhibiting dye transfer according to claim 19 which is carried out at a temperature in the range of from 5°C to 90°C.
- A process for inhibiting dye transfer according to claims 20-21 wherein the pH of the bleaching bath is from 7 to 11.
- A process for inhibiting dye transfer according to claim 21 wherein the pH of the bleaching bath is from 7 to 9.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920870019 EP0553608B1 (en) | 1992-01-31 | 1992-01-31 | Detergent compositions inhibiting dye transfer in washing |
US08/307,735 US5474576A (en) | 1992-01-31 | 1993-01-22 | Detergent compositions inhibiting dye transfer in washing |
CA 2127096 CA2127096C (en) | 1992-01-31 | 1993-01-22 | Detergent compositions inhibiting dye transfer containing a catalyst, amine stabilizer and peroxide generating enzyme |
PCT/US1993/000626 WO1993015176A1 (en) | 1992-01-31 | 1993-01-22 | Detergent compositions inhibiting dye transfer containing a catalyst, amine stabilizer and peroxide generating enzyme |
JP5513361A JPH07503278A (en) | 1992-01-31 | 1993-01-22 | A detergent composition containing a catalyst, an amine stabilizer, and a peroxide-generating enzyme and inhibiting dye migration. |
TR6993A TR26405A (en) | 1992-01-31 | 1993-01-22 | DETERGENT COMPOSITIONS THAT PREVENT DYEING THROUGH WASH |
PH45615A PH30907A (en) | 1992-01-31 | 1993-01-26 | Detergent compositions inhibiting dye transfer in washing. |
MX9300514A MX9300514A (en) | 1992-01-31 | 1993-01-29 | DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYE DURING LAUNDRY. |
CN 93102396 CN1075502A (en) | 1992-01-31 | 1993-01-30 | The detergent composition of dye transfer when suppressing washing |
AU48626/93A AU4862693A (en) | 1992-01-31 | 1993-09-28 | Detergent compositions inhibiting dye transfer in washing |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920870019 EP0553608B1 (en) | 1992-01-31 | 1992-01-31 | Detergent compositions inhibiting dye transfer in washing |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0553608A1 EP0553608A1 (en) | 1993-08-04 |
EP0553608B1 true EP0553608B1 (en) | 1998-06-17 |
Family
ID=8212238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19920870019 Expired - Lifetime EP0553608B1 (en) | 1992-01-31 | 1992-01-31 | Detergent compositions inhibiting dye transfer in washing |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0553608B1 (en) |
JP (1) | JPH07503278A (en) |
CN (1) | CN1075502A (en) |
AU (1) | AU4862693A (en) |
CA (1) | CA2127096C (en) |
MX (1) | MX9300514A (en) |
PH (1) | PH30907A (en) |
TR (1) | TR26405A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0593406A1 (en) * | 1992-10-13 | 1994-04-20 | The Procter & Gamble Company | Non-aqueous liquid detergent compositions |
DE19721886A1 (en) | 1997-05-26 | 1998-12-03 | Henkel Kgaa | Bleaching system |
CN101922111B (en) * | 2010-09-14 | 2012-05-09 | 东华大学 | Low-temperature activating and bleaching method by using water-soluble metalloporphyrin |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1541576A (en) * | 1975-06-20 | 1979-03-07 | Procter & Gamble Ltd | Inhibiting dye ltransfer in washing |
EP0308101B1 (en) * | 1987-09-08 | 1992-07-22 | Texaco Development Corporation | Preparation of tertiary butyl alcohol |
GB8826401D0 (en) * | 1988-11-11 | 1988-12-14 | Unilever Plc | Bleach composition |
ES2075132T3 (en) * | 1989-02-22 | 1995-10-01 | Unilever Nv | USE OF METAL-PORPHYRINS AS BLEACHING CATALYSTS. |
PE14291A1 (en) * | 1989-10-13 | 1991-04-27 | Novo Nordisk As | PROCEDURE TO INHIBIT THE TRANSFER OF DYES |
US4978799A (en) * | 1989-10-30 | 1990-12-18 | Texaco Chemical Company | Production of detergent range alcohols and ketones using porphyrin catalysts |
-
1992
- 1992-01-31 EP EP19920870019 patent/EP0553608B1/en not_active Expired - Lifetime
-
1993
- 1993-01-22 JP JP5513361A patent/JPH07503278A/en not_active Withdrawn
- 1993-01-22 TR TR6993A patent/TR26405A/en unknown
- 1993-01-22 CA CA 2127096 patent/CA2127096C/en not_active Expired - Fee Related
- 1993-01-26 PH PH45615A patent/PH30907A/en unknown
- 1993-01-29 MX MX9300514A patent/MX9300514A/en not_active IP Right Cessation
- 1993-01-30 CN CN 93102396 patent/CN1075502A/en active Pending
- 1993-09-28 AU AU48626/93A patent/AU4862693A/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CA2127096C (en) | 1998-04-14 |
JPH07503278A (en) | 1995-04-06 |
TR26405A (en) | 1995-03-15 |
EP0553608A1 (en) | 1993-08-04 |
CN1075502A (en) | 1993-08-25 |
CA2127096A1 (en) | 1993-08-05 |
AU4862693A (en) | 1994-07-07 |
MX9300514A (en) | 1994-07-29 |
PH30907A (en) | 1997-12-23 |
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