Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/13—Fugitive dyeing or stripping dyes
  • D06P5/132—Fugitive dyeing or stripping dyes with oxidants
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—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
• • 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
  • C11D3/3947—Liquid compositions
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/13—Fugitive dyeing or stripping dyes
  • D06P5/137—Fugitive dyeing or stripping dyes with other compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/15—Locally discharging the dyes
  • D06P5/153—Locally discharging the dyes with oxidants
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/15—Locally discharging the dyes
  • D06P5/158—Locally discharging the dyes with other compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
  • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/1026—Other features in bleaching processes
  • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/16—Bleaching ; Apparatus therefor with per compounds
  • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds

Definitions

• the invention relates to new storage-stable formulations, the at least one Peroxide compound, at least one mediator and at least one pH stabilizer contain, their production and their use in enzymatic bleaching systems, special enzymatic 2-component bleaching systems and their Use.
• enzymatic bleaching systems are known to the person skilled in the art Method for oxidative degradation or for changing a wide variety of substances.
• WO-A-92/18687 is used as an application for such enzymatic Bleaching systems, for example, described the decolorization of dyes.
• WO-A-94/29425 also describes the use together with active detergents Known substances. Also found in pulp bleaching in the paper industry enzymatic bleaching systems widely used (Journal of Biotech. 53 (1997) 163-202).
• the enzymatic bleaching systems are multi-component systems and settle down usually together from an enzyme, an oxidizing agent, one as Mediator designated auxiliary component and other additives such as pH regulators or auxiliary mediators.
• mediators come from the Group of aliphatic, cycloaliphatic, heterocyclic and aromatic Compounds containing NO, NOH or H-RN-OH.
• 1-hydoxybenzotriazole (HOBT) is widely mentioned as a mediator.
• Oxidizing agents are e.g. Hydrogen peroxide itself or peroxide sources such as perborate, persulfate or percarbonate.
• WO-A-94/29425 describes a multi-component bleaching system Use with washing-active substances described, which consists of an oxidation catalyst (e.g. in the form of an enzyme), an oxidizing agent and one Mediator exists. These three components form a common wording made in a washing solution.
• WO-A-99/34054 also describes a process for removing excess Known dye from a freshly dyed textile material.
• This method involves treating the dyed textile material with a washing solution which at least one enzyme with laccase or peroxidase activity, an oxidizing agent, contains at least one mediator and optionally further additives.
• a washing solution which at least one enzyme with laccase or peroxidase activity, an oxidizing agent, contains at least one mediator and optionally further additives.
• the said multi-component system of the washing solution in at least one of the Washing steps are added.
• the condition of the individual components is not critical, i.e. the individual components can each as a solution, as Slurry or used as granules. It is also stated that in a Embodiment a common formulation of the two enzyme components and mediator is manufactured, e.g.
• the multi-component system is a mixture of granules, with a granule component the enzyme and another granule component contains the mediator.
• WO-A-99/34054 is a preferred embodiment of the method in that First add a phosphate buffer to the washing liquor in one of the washing steps, then rinse with this wash liquor for a certain time and then the Components peroxidase, hydroxybenzotriazole and hydrogen peroxide simultaneously add individually. This single but simultaneous addition of the necessary Components represents when the process is carried out on an industrial scale high demands on the accuracy and timing of dosing.
• liquid product forms are in demand because they also affect each other automatic systems dosed precisely and reproducibly. Furthermore, one good storage stability even at higher temperatures is an important point for you successful industrial use.
• the object of the present invention was therefore to ensure storage stability and user-friendly formulations of enzymatic bleaching systems for one to find industrial use.
• the task was solved by the fact that a common formulation was achieved from at least one mediator, at least one peroxide compound and a pH stabilizer to provide.
• the common formulations of components a), b) and c) show an unexpectedly good storage stability. This is particularly surprising because because it is known that peroxide compounds in aqueous formulations generally show poor storage stability. Especially at higher storage temperatures degradation occurs more or less quickly and is associated with it an oxygen elimination of the peroxide compounds.
• aqueous peroxide formulations with stabilizers such as To add sodium phosphates or complexing agents.
• stabilizers such as To add sodium phosphates or complexing agents.
• formulations point to such, only with sodium phosphate stabilized formulations a further unexpectedly improved storage stability on.
• the radicals R 1 to R 4 can be substituted by one or more radicals R 9 , where R 9 is hydrogen, halogen, preferably fluorine, chlorine or bromine, hydroxyl, Formyl, amino, nitro, straight-chain or branched C 1 -C 12 alkyl, straight-chain or branched C 1 -C 6 alkoxy, carbonyl-C 1 -C 6 alkyl, phenyl, benzyl, phenyloxy, -COOR 5 , -SO 2 OR 5 , -SO 2 NH 2 , -NHSO 2 , -CONH 2 , -PO (OR 5 ) 2 , -PO 2 (OR 5 ) or -OPO (OR 5 ) 2 , means, where R 5 is already for has the meanings mentioned for formula (I).
• the radicals R 1 to R 4 can be substituted by one or more radicals R 9 , where R 9 is hydrogen, halogen, preferably fluorine, chlorine or bromine, hydroxyl, formyl, amino, Nitro, straight-chain or branched C 1 -C 12 -alkyl, straight-chain or branched C 1 -C 6 -alkoxy, carbonyl-C 1 -C 6 -alkyl, phenyl, benzyl, phenyloxy, -COOR 5 , -SO 2 OR 5 , -SO 2 NH 2 , -NHSO 2 , -CONH 2 , -PO (OR 5 ) 2 , -PO 2 (OR 5 ) or -OPO (OR 5 ) 2 , where R 5 is the same as for formula (I ) mentioned meanings.
• peroxide compounds as component b) of the formulations according to the invention it is hydrogen peroxide, hydrogen peroxide addition compounds such as peroxide-urea adducts, per-compounds such as perborates, percarbonates or persulfates in the form of their alkali salts, or mixtures thereof.
• Formulations are aqueous solutions from Buffer salts such as alkali metal, preferably sodium or potassium, phosphates, citrates, acetates, formates, borates or mixtures thereof.
• Buffer salts such as alkali metal, preferably sodium or potassium, phosphates, citrates, acetates, formates, borates or mixtures thereof.
• pH stabilizers show a stabilizing in the pH range of the optimal enzyme action Effect.
• the pH range of the aqueous solutions of the buffer salts is 3 - 9, preferably 4-7 and particularly preferably 5-6.
• the concentrations of the buffer salts in the aqueous solution are in the range of 0.5 - 2.0 mol / l, preferably in the range of 0.8 - 1.8 mol / l.
• suitable buffer salts are trisodium or Tripotassium phosphate, disodium or dipotassium hydrogen phosphate, sodium or Potassium dihydrogen phosphate, trisodium or tripotassium citrate, disodium or dipotassium citrate, Monosodium or monopotassium citrate, sodium or potassium acetate, Sodium or potassium formate, sodium or potassium tetraborate or mixtures thereof.
• the aqueous formulations according to the invention can a), b) and c) also contain conventional additives, e.g. Defoamers, surfactants, solubilizers such as glycols and polyethylene glycols or water conditioning agents like water softener.
• additives e.g. Defoamers, surfactants, solubilizers such as glycols and polyethylene glycols or water conditioning agents like water softener.
• Such additives are 0-20% by weight, preferably 0.5-15 % By weight, particularly preferably 1-10% by weight, based on the overall formulation used.
• the formulations according to the invention are prepared by mixing the three components a), b) and c) and optionally the further additives in in any order.
• the mediator of formula (I) and Per connections such as Solid sodium perborate to be used while Hydrogen peroxide is added as an aqueous solution.
• Hydrogen peroxide Usually used as a 3-50%, preferably 30-40% aqueous solution. It has also proven that the temperature of the formulation during the Mixing does not exceed 30 ° C.
• the pH of the formulations according to the invention is in the range 3-9, preferably 4-7 and particularly preferably 5-6.
• the invention furthermore relates to the use of the formulations according to the invention as a component of enzymatic bleaching systems.
• Another object of the invention is an enzymatic 2-component bleaching system, that as a component the aqueous formulation described above contains and as a second component at least one enzyme which is a peroxidase or Shows laccase activity.
• Enzymes with peroxidase activity can be used, for example are: All peroxidases of the enzyme classification (EC 1.11.1.7), haloperoxidases such as. Chloride peroxidases (EC 1.11.1.10) or any fragment or each synthetic or semi-synthetic derivative of this, which has peroxidase activity shows.
• Such enzymes are known and can be microbial, vegetable or be of animal origin.
• Formulations used as enzyme component such as peroxidases, which are produced by plants (e.g. horseradish or soybean peroxidase) or via microorganisms such as Bacteria or fungi.
• Some preferred fungi include strains belonging to the Deuteromycotina subgroup, Class of Hyphomycetes, such as Fusarium, humicola, Tricoderma, Myrothecium, Verticillum, Arthromyces, Caldariomyces, Ulocladium, Embellisia, Cladosporium or Dreschlera.
• Class of Hyphomycetes such as Fusarium, humicola, Tricoderma, Myrothecium, Verticillum, Arthromyces, Caldariomyces, Ulocladium, Embellisia, Cladosporium or Dreschlera.
• Fusarium are particularly preferred oxysporum (DSM 2672), Humicola insolens, Trichoderma resii, Myrothecium verrucana (IFO 6113), Verticillum alboatrum, Verticillum dahlia, Arthromyces ramosus (FERM P-7754), Caldariomyces fumago, Ulocladium chartarum, Embellisia alli or Dreschlera halodes.
• fungi include strains belonging to the Basidiomycotina subgroup, Class Basidiomycetes, belong e.g. Coprinus, Phanerochaete, Coriolus or Trametes, especially Coprinus cinereus f. microsporus (IFO 8371), Coprinus macrorhizus, Phanerochaete chrysosporium (e.g. NA-12) or Trametes such as. Trametes versicolor (e.g. PR4 28-A)
• Basidiomycotina subgroup Class Basidiomycetes, belong e.g. Coprinus, Phanerochaete, Coriolus or Trametes, especially Coprinus cinereus f. microsporus (IFO 8371), Coprinus macrorhizus, Phanerochaete chrysosporium (e.g. NA-12) or Trametes such as. Trametes versicolor (e.g. PR4 28-A)
• Fungi further preferred for peroxidase production include strains which belong to the subgroup Zygomycotina, class Mycoraceae, e.g. Rhizopus or Mucor, especially Mucor hiemalis.
• Some preferred bacteria include strains of the Actinomycetales such as e.g. Streptomyces spheroides (ATTC 23965), Streptomyces thermoviolaceus (IFO 12382) or Streptoverticillum verticillium ssp. verticillium.
• Actinomycetales such as e.g. Streptomyces spheroides (ATTC 23965), Streptomyces thermoviolaceus (IFO 12382) or Streptoverticillum verticillium ssp. verticillium.
• Bacillus pumilus ATCC 12905
• Bacillus stearothermophilus Rhodobacter sphaeroides
• Rhodomonas palustri Rhodomonas palustri
• Streptococcus lactis Pseudomonase purrocinia
• Pseudomonas fluorescens NRRL B-11.
• strains belonging to Myxococcus such as. Myxococcus virescens.
• the peroxidase can also be produced by a method which the Culturing a guest cell containing a recombinant DNA vector.
• This recombinant DNA vector in turn contains a DNA sequence that is responsible for the Peroxidase encoded, as well as DNA sequences, which the expression of the Allow peroxidase coding DNA sequence.
• the cultivation takes place in one Culture medium under conditions that allow expression of the peroxidase.
• a peroxidase produced via recombinant DNA is particularly suitable from Coprinus sp., preferably Coprinus macrorhizus or Coprinus cinereus derives as described in WO-A-92/16634.
• Active peroxidase activity can also be used as a peroxidase component Fragments derived from cytochrome, or hemoglobin are used synthetic or semi-synthetic derivatives thereof such as e.g. Iron complexes of Porphyrins or phthalocyanines or derivatives thereof.
• enzymes with laccase activity can be used: all Enzyme classification laccases (EC 1.10.3.2), each catechol oxidase Enzyme classification (EC 1.10.3.1), any bilirubin oxidase from the enzyme classification (EC 1.3.3.5) or any monophenol monooxygenase of the enzyme classification (EC 1.14.99.1).
• laccases of plant or microbial origin are known.
• the microbial laccases are derived from bacteria or fungi. Suitable examples include laccases derived from voices of the Aspergillus, Neurospora, e.g.
• laccases derived from strains of Fomes, Trametes, Rhizoctonis, Derive Coprinus, Myceliophthora, Schytalidium or Polyporus.
• the laccase can also be produced by a process which the Culturing a guest cell containing a recombinant DNA vector.
• This DNA vector in turn contains a DNA sequence necessary for laccase encoded, as well as DNA sequences which express the expression of the laccase Allow DNA sequence. The cultivation takes place in a culture medium under Conditions that allow expression of laccase
• aqueous solution according to the invention is preferred first Formulation and then added the enzyme component.
• formulations according to the invention is particularly preferred as Component of an enzymatic 2-component bleaching system for decolorization of excess, unbound dye from textile materials after a Coloring.
• the invention thus also relates to a method for removing excess unbound dye of textile materials after dyeing, preferably reactive dyeing, characterized in that the colored material in one or more of the rinsing steps following the coloring with the enzymatic 2-component bleaching system is brought into contact by the two components in any order, but sequentially in time Rinse liquor clogged.
• the dyed textile materials can be natural materials such as e.g. Cotton, viscose, rayon, lyocell, wool or silk, or synthetic Materials such as Polyester, polyamide or polyacrylonitrile, or mixtures act from natural and synthetic materials. Particularly preferred are cotton, viscose and lyocell or their blends with Polyester and polyamide.
• the procedure to remove the excess unbound dye is Usually carried out at a temperature of 25-80 ° C, preferably 40-60 ° C.
• the pH in the washing liquor is in the range of 3-9, preferably 4-8 and especially preferably 5-7.
• the enzyme is usually used as an aqueous solution in such an amount added that 0.005-5 mg enzyme per liter of washing liquor, preferably 0.02-2 mg Enzyme per liter of washing liquor and particularly preferably 0.05-1 mg of enzyme per liter Wash liquor are available.
• the aqueous solution of the enzyme can optionally contain other common additives such as e.g. Monopropylene glycol.
• the formulation according to the invention is preferred in an amount of 0.1-10 g 0.5-2.5 g per liter of washing liquor added.
• the invention Add aqueous formulation and then only when the aqueous formulation evenly distributed in the wash liquor, the enzyme component add as a second component.
• This way of adding can Surprisingly, a significantly stronger oxidative degradation of the dye in the Wash liquor can be achieved when using the method of WO-A-99/34054 Large-scale implementation is possible if the enzyme, the mediator and the Peroxide compound individually and at the same time added to the washing liquor. This Implementation according to WO-A-99/34054 seems to be an disadvantageous deactivation of the enzyme.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Biochemistry (AREA)
• Microbiology (AREA)
• Detergent Compositions (AREA)

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• 1999
  • 1999-10-12 DE DE19948989A patent/DE19948989A1/de not_active Ceased
• 2000
  • 2000-09-29 DE DE2000508895 patent/DE50008895D1/de not_active Expired - Lifetime
  • 2000-09-29 EP EP00121206A patent/EP1092762B1/fr not_active Expired - Lifetime
  • 2000-10-04 US US09/678,599 patent/US6380142B1/en not_active Expired - Fee Related

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