DE102006055669A1 - Enzyme preparation with carrier-bound antioxidants - Google Patents

Enzyme preparation with carrier-bound antioxidants

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Publication number
DE102006055669A1
DE102006055669A1 DE200610055669 DE102006055669A DE102006055669A1 DE 102006055669 A1 DE102006055669 A1 DE 102006055669A1 DE 200610055669 DE200610055669 DE 200610055669 DE 102006055669 A DE102006055669 A DE 102006055669A DE 102006055669 A1 DE102006055669 A1 DE 102006055669A1
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DE
Germany
Prior art keywords
acid
characterized
carrier
preparation according
enzyme
Prior art date
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Withdrawn
Application number
DE200610055669
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German (de)
Inventor
Andre HÄTZELT
Peter Dr. Schmiedel
Christian Umbreit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to DE200610055669 priority Critical patent/DE102006055669A1/en
Publication of DE102006055669A1 publication Critical patent/DE102006055669A1/en
Application status is Withdrawn legal-status Critical

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38672Granulated or coated enzymes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0084Antioxidants; Free-radical scavengers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/1213Oxides, hydroxides, e.g. Al2O3, TiO2, CaO, Ca(OH)2
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2096Heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid, cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides; Polyimides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Abstract

The invention relates to enzyme preparations in granular form, which contain a carrier-bound antioxidant, as well as new, carrier-bound antioxidants and liquid washing-active preparations which simultaneously contain a solid enzyme granules and a bleaching agent.

Description

  • object The invention are enzyme preparations in granular form, which are a carrier-bound Contain antioxidants, as well as new, carrier-bound Antioxidants and liquid detergent compositions, which at the same time contain a solid enzyme granulate and a bleaching agent.
  • enzyme preparations have gained importance in many fields of technology. So they are used in detergents and cleaners to improve the Performance especially against enzymatic degradable soils such as proteins, starch and the like used. However, enzymes are known to be complex Proteins easily lose their performance due to chemical influences. This is especially true when bleaches are present.
  • In the international application WO 00/27978 A1 discloses liquid detergents and cleaners which contain antioxidants as radical scavengers to protect against oxidation reactions which are triggered by free radicals. Suitable radical scavengers, for example, polyhydroxybenzoic acids are listed in this document. Such antioxidants protect the enzyme. The disadvantage, however, is that they often have a negative influence on the bleach system. This applies in particular to modern bleaching agents such as phthalimidohexane percarboxylic acid (PAP).
  • From the European patent application EP 0290223 are known preparations of hydrolytic enzymes and bleaching agents containing such preparations. There are proposed there particulate enzyme products containing a core in which the hydrolytic enzyme is located and a coating layer comprising this core, wherein the coating layer contains a substance which reacts with oxidizing agents, deactivate the enzymes. The enzyme protection agent is selected from the group of alkali salts, mixtures of alkali salts with a pH> 10, the reducing agent, the antioxidant and the transition metal complexes.
  • In front Background of this prior art, the inventors have tasked to provide antioxidants that as constituents of enzyme granules even then not for degradation of bleaches, if these at the same time as a disperse phase are present in the same product matrix.
  • The Solution of this problem is achieved by enzyme preparations in granular form, containing one or more enzymatically active Proteins and, if desired, adsorbents, granulating aids and / or coating agent, characterized in that above an effective amount of a carrier-bound antioxidant is included.
  • In a general embodiment, the invention relates thus carrier-bound antioxidants. For the purposes of the invention are preferably carrier-bound Antioxidant based on low molecular weight antioxidants those via free hydroxyl groups or carboxylic acid groups with which they are esterified by organic Carrier or by salt formation on inorganic carriers ge can be tied. Under free hydroxyl groups respectively Carboxylic acid groups are understood here to mean such groups with an organic acid or a Alcohol can be converted to an ester without causing the antioxidant Properties of the reaction product are lost. Suitable antioxidants are naturally occurring antioxidants, for example, those used in the food industry especially antioxidants such as tocopherol, its derivatives, ascorbic acid and the same. Another important class is phenolic antioxidants. These are hydroxyphenyl compounds with at least one other Substituents, in particular an OH group or carboxyl group, preference is given to compounds which form quinoidal structures can. Among these compounds are di- and trihydroxybenzoic acids preferred, especially gallic acid.
  • According to the invention the antioxidants bound to carriers. To this Connection is a variety of chemical reactions suitable, the preferably to covalent bonds between the antioxidant and lead the carrier. Particularly preferred it, corresponding antioxidants by ester bonding to a Tie wearers.
  • A According to the invention preferred class carrier-bound Antioxidants are esters of acid group-containing Antioxidants such as the aforementioned hydroxybenzoic acids or ascorbic acid and polymers having hydroxyl groups.
  • As polymers with hydroxyl groups can thereby polymers, that is by radical polyme polymers, polycondensates, that is to say those produced by esterification, amide formation and the like, addition polymers, that is to say polymers which can be prepared by reacting diisocyanates and diols and similar reactions, or else naturally occurring polymers, such as, for example, polysaccharides, lignin and the like can be used. The said polymers are reacted under conventional esterification conditions with the antioxidants.
  • To Another embodiment of the invention will be Antioxidants in acid form to basic surfaces inorganic substances capable of salt formation, added. So you can, for example, ascorbic acid or hydroxybenzoic acids, in particular gallic acid, on finely divided solid inorganic oxides salt-like or covalently bound. Suitable oxides are oxides and or oxide hydrates, and or hydroxides of aluminum, zinc, Titans and or the silicon.
  • To In a particularly preferred embodiment, the aforementioned acid group-containing antioxidant esterified with polymers having hydroxyl groups. So can For example, homopolymers or copolymers of hydroxyethyl acrylate or hydroxyethyl methacylate with the corresponding acids implement. After a likewise particularly preferred procedure starting from polyvinyl acetate, the at least partially to Polyvinyl alcohol is saponified then followed by the Polyvinyl alcohol with the acid group of the antioxidant is esterified.
  • To a further preferred embodiment of the invention become the acids of the antioxidants with polyesters, Polyamides or polyurethanes which carry hydroxyl end groups, esterified. Corresponding polyesters, polyamides or polyurethanes can be linearly branched or hyperbranched. Highly branched products are due to their higher number of binding sites, based on the molecular weight, preferred.
  • To a further preferred embodiment of the invention become the antioxidants via hydroxyl groups bound polymeric acids. Suitable polymeric acids are, for example, homo- and copolymers of acrylic acid, methacrylic acid, itaconic acid or maleic acid. In the latter case, particular preference is given to copolymers which Contain maleic anhydride structures, which then become with the OH groups of, for example, ascorbic acid or let the gallic acid ring open.
  • To a further preferred embodiment of the invention The low molecular weight antioxidants are controlled by their acid groups hydroxyl-containing polymers of natural origin such as starch, cellulose, guar or their synthetic etherification products bound. In particular, such natural hydroxyl-containing polymers to the inventive Antioxidant compounds are reacted, usually as a carrier for enzyme in enzyme granules be used, such as starch, cornmeal and the same.
  • According to the invention, the carrier-bound antioxidants are used in enzyme granules. According to a first embodiment of the invention, they can be used in enzyme granules, as described for example in the patent application WO 97/40128 are described. According to this application enzyme granules are prepared by a process in which an aqueous enzyme-containing liquid with inorganic and / or organic support material and granulation aids is processed as aggregates to a premix, which is subjected to an extrusion step, whereupon extrudates with a grain size of 0.3-3 are then optionally subjected to a Sphäronisierungsschritt in a Rondiergerät and optionally a drying step. Preference is given to products on which subsequent coatings are applied, which may also contain dyes or pigments. The enzyme preparations described there contain phosphatized starch and / or polyethylene glycol and polysaccharides, such as, for example, sucrose, cereal flour or cellulose powder as support material, as granulation aids. The support-bound antioxidants according to the invention can be mixed with such granules, or they are sprayed after the extrusion process as a solution in a suitable solvent or applied by powdering or other measures on the surface.
  • According to a further preferred embodiment of the invention, the carrier-bound antioxidants can be used in granules which are suitable for liquid detergents or liquid cleaning agents. Such granules generally have a multilayer structure. They contain an enzyme, a low-density filler and an outer coating agent. Particularly preferred are granules, as in the international application WO 00/29534 are described. The granules mentioned there are adjusted to low dust and have a true density of less than 1.4 g / cm 3 , so that they are dispersible in the liquid detergents and cleaners without sedimentation. Regarding the manufacturer ment of such granules is based on the teaching of said WO 00/29534 directed. Thereafter, for example, a carrier material such as sucrose can be placed in a fluid-bed reactor and processed to a granulate with a liquid preparation of starch, sucrose and water. This is then applied to the protease solution and finally coated with a preparation containing titanium dioxide, methyl cellulose, polyethylene glycol and / or surfactants. In this process, the antioxidants according to the invention are preferably dissolved or dispersed in the coating composition and then applied to a cover layer when the enzyme granules are coated.
  • According to a further preferred embodiment, the carrier-bound antioxidants are used in enzyme granules, as described in the international application WO 01/23513 are described. The enzyme particles described there contain a solid wax matrix of at least two solid waxes in which the active enzyme particles are dispersed. With regard to individual embodiments and the preparation of such enzyme granules, which in turn are particularly suitable for liquid detergents, reference is made to the cited WO 01/23513 directed. The carrier-bound antioxidants of the present invention can either be added to the active dispersed enzyme grains in this embodiment, or they can be dissolved or dispersed in the wax matrix.
  • Generally preferred are enzyme granules according to the invention with a grain size of 0.1 mm to 2 mm, containing From 2% to 20% by weight of protease, lipase, amylase and / or cellulase, calculated as dry substance, 10 wt .-% to 50 wt .-% swellable Starch, 5 wt .-% to 50 wt .-% Granulierhilfsmittel, the contains water-soluble organic polymer, not over 10% by weight of water-soluble salt and 3% by weight to 12% by weight Water containing 10% to 35% by weight of cereal flour.
  • To a further preferred embodiment include the enzyme granules according to the invention, natural, formed by the microorganisms used for fermentation, stabilizing impurities.
  • The Enzyme granules of the invention can furthermore adsorbents, granulating aids, such as Binder or plasticizer, and / or coating agent contain.
  • According to another preferred embodiment, the enzyme granules according to the invention in addition to the carrier-bound antioxidant, the following ingredients:
    • (a) an enzyme
    • (b) a particulate carrier material as adsorbent,
    • (c) one of (b) different ingredient as binder and
    • (d) optionally further ingredients other than (b) and (c),
    and does not substantially disintegrate when stored at 23 ° C in an aqueous buffer system consisting of 16% sodium sulfate and 3% sodium citrate in water, pH 5.0 ± 0.1 over a period of 24 hours.
  • Particularly preferred are the following quantity ranges for the components mentioned:
    • (a) 5-99% by weight of the active substance of the enzyme,
    • (b) 10-80% by weight of a particulate carrier material (adsorbent),
    • (c) 3-50% by weight of one of (b) different ingredients as a binder and
    • (d) as optional further, different from (b) and (c) ingredients: 0-50 wt .-% (based on the granules) plasticizer, 0-50 wt .-% (based on the granules) disintegration aid and / or 0-40 wt .-% (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, antioxidants, the density regulating compounds and / or other ingredients.
  • preferred Components (b) (adsorbents) are one or more of the compounds selected from the group: talc, silicic acid, Alumina, silicate, in particular phyllosilicate and / or sodium aluminosilicate, Bentonite, aluminosilicate (zeolite), sulfate, titanium dioxide and / or polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA, particularly preferred a combination of two or three of these compounds.
  • preferred Components (c) (binders) are one or more of the compounds selected from the group: polyacrylate, polymethacrylate, Polyvinylpyrrolidone, polysaccharide or substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of mentioned compounds, in particular methacrylic acid-ethyl acrylate copolymer, especially preferably a combination of two or three of these compounds.
  • Prefers as part of component (d) (plasticizer) are one or more Compounds selected from the group: water-dispersible organic compound or water-dispersible organic polymer, especially polyethylene glycol (PEG), especially short chain PEG, fatty acid or salt of a fatty acid, triacetin, Triethyl citrate and / or polyhydric alcohol, preferably fatty acid or salt of a fatty acid, more preferably sodium stearate and / or sodium oleate.
  • Prefers as part of component (d) (disintegration aids) are a or more compounds selected from the group: water-soluble inorganic salt, monosaccharide, in particular glucose, oligosaccharide, Polysaccharide, in particular cellulose, compacted cellulose or Cellulose derivative, crosslinked organic polymer, in particular crosslinked polyvinylpyrrolidone or crosslinked polyacrylate.
  • The Antioxidants according to the invention can also be used in granules of the core / shell type. such Granules of the so-called core / shell type as well as processes and apparatus for their preparation are known per se. The manufacturing process are usually reflected in the structure of the coating again. Overviews about These methods and apparatus provide relevant manuals. In a suitable coating process, the granules particles, preferably enzyme particles, presented in the hot air stream and sprayed over a top sprayer, the coating material. This is done under drying conditions, that is 40-45 ° C, so that the product is about 35-38 ° C and dry remains.
  • preferred Core-shell granules are those in which the enzyme granules particles with an aqueous emulsion based on silicone oil have been coated.
  • Also suitable are the enzyme granulate particles which are coated with a polymer solution containing inorganic pigment and which contain the carrier-bound antioxidants present according to the invention. Preferred coating agents with which the antioxidants present according to the invention can be applied
    • (1) a pigment-containing coating of: (a) 5 to 70% by weight (based on the coating) of fine, inorganic, water-insoluble pigment, (b) 45 to 90% by weight of an organic substance having a melting point of 40 to 70 ° C and (c) to 20% by weight of a bulkiness improving agent;
    • (2) a coating containing a polyvalent metal salt of a straight or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms is applied.
    • (3) applying a mixture of TiO 2 , urea and polyethylene glycol having a water content of less than 50% by weight.
    • (4) emulsions based on silicone oil, these being in the form of water-in-oil emulsions (W / O), oil-in-water emulsions (O / W), multiple emulsions (W / O / W) and Nano and microemulsions are applied.
    • (5) abrasion-resistant coated enzyme granules, which can be prepared by subjecting the granules particles with a urea-containing aqueous preparation and the water at least partially removed by drying. Advantageously, according to this application, the fines of the initially coated uncoated granules are first removed via a two-stage air classification and then the very abrasion-resistant layer of urea / PEG / TiO 2 having a water content of less than 50% is applied.
  • According to one further embodiment of the present invention it is a coated granulate, the coating too more than 50% by weight of one or more of the following compounds consists of: water-dispersible substances, water-dispersible and / or water-soluble polymer, fatty acid, salt of a Fatty acid, fatty alcohol, paraffin, polyvinyl acetate, polyacrylate, Polymethacrylate, methacrylic acid-ethyl acrylate copolymer, Polyvinylpyrrolidone, cellulose ethers, polyvinyl alcohol and ethoxylated Polyvinyl alcohol.
  • Favorable is that, granules of the invention with a additional polymer coating increased stability values exhibit.
  • According to one Another preferred embodiment is an inventive polymer-coated Granules, wherein the water-soluble polymer polyacrylate or a methacrylic acid-ethyl acrylate copolymer and / or the cellulose ether is methyl cellulose (MC), Hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) or carboxymethylcellulose (CMC).
  • To a further preferred embodiment the coating additionally one or more fillers selected from the group of inorganic particles, preferably Silicate or alumina, more preferably talc.
  • To a further preferred embodiment the coating additionally one or more plasticizers, selected from the group: triethyl citrate, triacetin, polyfunctional Alcohol, especially 1,2-propanediol, and polyethylene glycol.
  • In a preferred embodiment of the present invention have the uncoated or inventive coated granules have a mean particle diameter of 100 to 3,000 μm, preferably 200 to 2,500 μm, more preferably 400 to 2,000 μm.
  • According to one preferred embodiment of the present invention have the uncoated or inventive Coated granules have an average density of 1.00 to 1.50, preferably from 1.02 to 1.30, more preferably from 1.05 to 1.15 g / ml.
  • According to one Another embodiment can according to the invention Granules more than one, covalently bonded to a support Antioxidant and / or various support materials with the same antioxidants and / or several antioxidants bound contained on the same carrier material. advantageously, complement each other in terms of their reducing power, d. H. cover certain spectrum and / or a certain response in terms of preferred substrates. So are some connections particularly well suited for protection against atmospheric oxygen while other particularly well-contained in the mixture oxidizer to inactivate.
  • In In another embodiment, inventive Granules additionally, not covalently attached to a carrier contain bound antioxidants to one as possible to exert comprehensive oxidation protection. Because it can be straight Intended to be antioxidant over the solid granules diffuse into fiction-relevant means and there, d. H. outside to allow the granules of the invention to act.
  • The granules of the invention contain the active enzyme in amounts of up to 20 wt .-%. The skilled person will preferably adjust the amount of enzyme such that the total preparation, for example the liquid detergent containing the granules, has some amount between 1 × 10 -8 and 5% by weight of active protein.
  • The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).
  • Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) derive from the name under the name BLAP ® variants, which in particular in WO 92/21760 A1 . WO 95/23221 A1 . WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications WO 03/054185 A1 . WO 03/056017 A2 . WO 03/055974 A2 and WO 03/054184 A1 out.
  • Other usable proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozyme ® from Novozymes, the ® under the trade names Purafect ®, Purafect ® OxP, Purafect Prime and Properase.RTM ® from Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, the P under the trade names Proleather® ® and protease ® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name proteinase K-16 from Kao Corp., Tokyo, Japan.
  • Examples of amylases which can be prepared according to the invention are the α-amylases from Bacillus licheni formis, from B. amyloliquefaciens or from B. stearothermophilus and their improved for use in detergents or cleaners further developments. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • Furthermore, for this purpose in the application WO 02/10356 A2 disclosed α-amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application WO 02/44350 A2 described cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Furthermore, the amylolytic enzymes belonging to the sequence space of α-amylases can be used, which in the application WO 03/002711 A2 is defined, and the ones in the application WO 03/054177 A2 to be discribed. Likewise, fusion products of said molecules can be used, for example those from the application DE 10138753 A1 or point mutations of it.
  • In addition, the enhancements available under the trade names Fungamyl.RTM ® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Further usable commercial products are, for example, the Amylase-LT ® and Stainzyme ® , Termamyl ® Ultra and Stainzyme ® Ultra, the latter also from the company Novozymes. Variants of these enzymes which can be obtained by point mutations can also be incorporated into granules according to the invention.
  • Granules of the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ® and Lipomax® ® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ®, Lipase OF ® and lipase PL ® to mention also the product Lumafast® ® from Genencor.
  • invention Granules can, especially if they are for the Treatment of textiles are thought to contain cellulases, ever after purpose as pure enzymes, as enzyme preparations or in the form of mixtures, in which the individual components advantageously with respect to their different performance aspects complete. These performance aspects include in particular Contributions to the primary washing performance, to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and conditioning (fabric effect), to the exercise of a "stone wash "effect.
  • A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ®. The products Endolase® ® and Carezyme ®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ® and Renozyme ®. The latter is based on the application WO 96/29397 A1 , Performance-enhanced cellulase variants go, for example, from the application WO 98/12307 A1 out. Likewise, those in the application WO 97/14804 A1 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®. Further commercial products from AB Enzymes are Econase® ® and ECOPULP ®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are in WO 96/34092 A2 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ® is available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and IndiAge ® Neutra.
  • Granules according to the invention for use in detergents or cleaners can, in particular for the removal of certain problem soiling, comprise further enzymes which are combined under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases example, under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes, under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA, and under the name Purabrite ® from Genencor Int., Inc., Palo Alto, CA, USA. A suitable β-glucanase from a B. alcalophilus, for example, from the application WO 99/06573 A1 out. The obtained from B. subtilis β-glucanase is available under the name Cereflo ® from Novozymes.
  • To increase the bleaching effect, granules according to the invention may also contain oxidoreductases, for example oxidases, oxygenases, catalases (which react as peroxidase at low H 2 O 2 concentrations), peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned. As an example of advantageous systems for an enzymatic perhydrolysis can be applied to the application WO 98/45398 A1 directed. For example, choline oxidases useful for such a system are disclosed WO 2004/058955 A2 , Modified proteases with pronounced, at this point also advantageously usable perhydrolase activity, in particular for achieving a mild bleaching in laundry detergents go from the application WO 2004/058961 A1 out. A combined enzymatic bleaching system comprising an oxidase and a perhydrolase describes the application PCT / EP 2005/006178 , Further perhydrolases which can be used according to the invention are also disclosed WO 2005/056782 A2 , Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • The disclosure of the abovementioned sequences of perhydrolases is based on the disclosure in the international patent application WO 2005/124012 A1 directed.
  • The used in granules of the invention enzymes are either originally from microorganisms, about genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or by filamentous Fungi.
  • Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. Among the above-mentioned commercial products Everlase ® and Purafect OxP as examples of such proteases and Duramyl are particular to cite as an example of such an α-amylase.
  • A preferred embodiment is an inventive Enzyme granules with an enzyme content of 5 to 99 wt .-% of active substance of the enzyme, increasingly preferably 5 to 90% by weight, 5.2 to 80% by weight, 5.4 to 70% by weight, 5.6 to 60% by weight, 5.8 to 50% by weight, 6.0 to 40% by weight, 6.2 to 30% by weight, 6.4 to 20% by weight, 6.6 to 17.5% by weight, 7.0 to 15 wt .-%, most preferably 10 to 12 wt .-% of active substance.
  • A preferred embodiment is an inventive Granules, being covalently attached to a supramolecular carrier bound antioxidant up to 30 wt .-%, preferably 10 to 20 wt .-%, particularly preferably from 12.5 to 17.5 wt .-% of the granules.
  • in this connection is it computational to the concentration of this invention essential Ingredient that is based solely on its substance concentration, d. H. without the covalent according to the invention bound supramolecular carrier. This size is important to the resulting antioxidant Adjust effect accordingly.
  • To a preferred embodiment, the inventive Enzyme granules in detergents and in particular in liquid detergents used. This shows the superior properties of products according to the invention especially if these liquid detergents additionally contain a bleaching agent.
  • Suitable liquid detergents are for example from WO 96/05284 A1 or the WO 99/28430 A1 known.
  • Next the enzyme granules contain the liquid washing and Detergent surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. Prefers are from an application point of view mixtures of anionic and nonionic surfactants.
  • When Nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used. In addition, you can as further nonionic surfactants also alkyl glycosides, alkoxylated Fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.
  • Of the Content of nonionic surfactants is in the liquid Washing and cleaning agents preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-%, each based on the entire remedy.
  • As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, alkane sulfonates and / or the esters of α-sulfo fatty acids (ester sulfonates). The surfactants of the sulfates type include, for example, alk (en) ylsulfates or ethoxylated alkenyl sulfates. Further suitable anionic surfactants are sulfated fatty acid glycerol esters and alkylsulfosuccinic acid salts.
  • Especially preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts lauric, myristic, palmitic, Stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • The anionic surfactants including soaps can in the form of their sodium, potassium or ammonium salts and as soluble Salts of organic bases, such as mono-, di- or triethanolamine, are present.
  • Of the Content of preferred liquid detergents and cleaners of anionic surfactants is 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the entire remedy.
  • additionally to the enzyme granules and to the surfactant (s) the liquid detergents and cleaners contain other ingredients included, which are the performance and / or aesthetic Properties of the liquid detergent and cleaner improve further. Included in the scope of the present invention preferred agents in addition to the enzyme granules and to the surfactant (s) one or more substances from the group of builders, Bleaching agents, bleach activators, electrolytes, non-aqueous Solvents, pH adjusters, fragrances, perfume carriers, Dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brightener, grayness inhibitors, dye transfer inhibitor, Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobizers and impregnating agents, swelling and anti-slip agents, and UV absorbers.
  • It is particularly preferred that the washing and cleaning agent contains a bleaching agent. Among the compounds serving as bleaches in water H 2 O 2 , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or organic peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N 'Terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures thereof. Preferred peracids include the phthalimidoperoxoalkanoic acids, especially 6-phthalimidoperoxohexanoic acid (PAP).
  • The Amount of bleach is preferably between 0.5 and 25 wt .-% based on the total washing and cleaning agent.
  • In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergents and cleaners. As a bleach activator compounds which give aliphatic peroxycarboxylic acids under perhydrolysis conditions can be used. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • additionally to the conventional bleach activators or in their place so-called bleach catalysts in the liquid washing and detergents are incorporated. These substances are these are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also, Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing Tripod ligands and Co, Fe, Cu and Ru ammine complexes are known as Bleach catalysts usable.
  • The Liquid detergents and cleaners are preferably substantially anhydrous. "Essentially anhydrous" means in the context of this Invention, that the agent produced is preferably not a free, not bound as crystal water or in comparable form Water contains a decomposition of an existing bleach to prevent. In some cases, small amounts are tolerable free water, especially in amounts up to 5 wt .-%.
  • The Enzyme granules can be stable in the liquid Washing and cleaning agents, for example by stirring, be dispersed. Stable means that the agent is at room temperature and at 40 ° C over a period of at least 4 weeks and preferably at least 6 weeks are stable, without that the enzyme granules cream or sediment or even disintegrate.
  • Examples
  • example 1
  • Formation of an inventive Antioxidant by binding to an organic polymer
  • Under an inert gas atmosphere and with exclusion of light 10.26 g of a solution of poly-2-hydroxyethyl acrylate (0.95 g polymer to 20 ml of solvent) in 350 ml of dioxane and with 70 g of p-toluenesulfonyl chloride and 55.72 g of triethylamine added and stirred for about 30 min. To this Solution are added 63.71 g of gallic acid and heated at 50 ° C for about 120 h. The solution is concentrated and purified by dialysis. The reaction product is completely dried by lyophilization.
  • hereby to obtain a covalent according to the invention antioxidant bound to a supramolecular carrier, in this case one to an organic polymer, viz a polyacrylate, bound gallic acid.
  • Example 2
  • Formation of another invention Antioxidant by binding to an organic polymer
  • To a solution of 5 g of the hydroxyl-hyperbranched polyesteramide Hybrane ® (DSM Hybrane BV, Heerlen, Netherlands), in 270 ml of dioxane, 5.34 g of gallic acid in 200 ml of dioxane and 2 mol were protected from light and inert% p-toluenesulfonic acid in 30 ml of dioxane. After addition of 20 g of dry commercial molecular sieve of sodium aluminosilicate (4 Angstrom molecular sieve, available from Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany) to remove small amounts of water, the mixture is slowly heated to 60 ° C and the reaction product after about 200 h cleaned by dialysis and lyophilized.
  • hereby to obtain a covalent according to the invention antioxidant bound to a supramolecular carrier, in this case one to an organic polymer, viz a hyperbranched polyester amide bound gallic acid.
  • Example 3
  • Formation of another invention Antioxidant by binding to an organic polymer
  • To a solution of 10 g of the hydroxyl-hyperbranched polyesteramide Hybrane ® from. Hybranes DSM BV and 13.19 g of 3,4,5-trimethoxybenzoic acid in 300 ml of chloroform was added under exclusion of light and inert gas atmosphere, 1 ml of sulfuric acid and slowly to about 60 ° C heated. After about 120 h, 20 ml of saturated sodium bicarbonate solution were added and the organic phase was freed from the solvent in vacuo.
  • The Reaction product was deprotected by boron tribromide and then by dialysis and freeze-drying as pale beige solid obtained.
  • hereby to obtain a covalent according to the invention antioxidant bound to a supramolecular carrier, in this case one to an organic polymer, viz a hyperbranched polyester amide bound 3,4,5-trimethoxybenzoic acid.
  • Example 4
  • Formation of an inventive Antioxidant by binding to inorganic particles
  • Under light exclusion 5.55 g of gallic acid with 300 ml of water are stirred in an inert atmosphere at about 30 ° C and slowly with 20 g of aluminum oxide (hydroxide) (trade name Disperal P3 ®;. Sasol, Hamburg, Germany) was added. It is heated for about three hours under reflux and separated after cooling, the solid, washed several times with water and then dried in vacuo.
  • hereby to obtain a covalent according to the invention antioxidant bound to a supramolecular carrier, in this case, an inorganic particle (aluminum hydroxide mixed oxide) bound gallic acid. Therein lies the gallic acid over a kind of ester bond attached to the particle.
  • One Example reaction product contained 21.8 % By weight of bound gallic acid, determined by the determination of the degree of occupancy via elemental analysis, corrected by the value of the educt (Disperal P3).
  • Example 5
  • Formation of another invention Antioxidant by binding to inorganic particles
  • Under Exclusion of light are in an inert gas atmosphere 58.73 g of dioctyl gallate in 600 ml of dioxane and submitted slowly added with stirring 130 g Disperal P3. The Reaction mixture is heated to reflux and after about four hours the solid separated after cooling, this washed with plenty of dioxane and diethyl ether and in vacuo freed from the remaining solvent.
  • hereby to obtain a covalent according to the invention antioxidant bound to a supramolecular carrier, in this case, an inorganic particle (aluminum hydroxide mixed oxide) over an ester bond bound Gallussäurederivat.
  • One Example reaction product contained 25.9% (w / w) bound octyl gallate, determined by the determination of the degree of occupancy via elemental analysis, corrected by the value of the educt (Disperal P3).
  • Example 6
  • Preparation of an inventive enzyme granulate
  • Granules (granules E1) are produced by extrusion from the following components: Quantity [g] ingredient 80 Partially hydrolyzed polyvinyl alcohol (Erkol M05 / 290, Wacker-Chemie, Munich) 140 Sodium stearate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 20 Sodium aluminum silicate (average particle size 3.5 microns; commercially available product ® Wessalith P = Wessalith ® 4000;. Degussa, Frankfurt / M., Germany) 80 Inventive carrier-fixed antioxidant according to Example 5 60 Titanium dioxide (Kronos, Leverkusen, Germany) 456 liquid protease concentrate (commercial product Everlase ® 6-8T; Novozymes, Bagværd, Denmark).
  • To All powdered and dry substances are premixed and with a powder metering in the extruder (twin-screw extruder Type 20 / 40D; Fa. Brabender, Duisburg, Germany). To a process length of 12 D is done using a laboratory metering pump type M5 Lewa Lab (Hermann Ott AG, Leonberg, Germany) the addition of the liquid enzyme. The promotion ratio of Powder dosage for liquid metering is 13: 0.6 to 13: 0.4. Subsequently, on a process length of 28 D homogenized and plasticized. For the packaging the enzyme mass is passed through a round rod nozzle (diameter 2 mm) on a conveyor belt and after a cooling section 1 m into a granulator. The resulting cylindrical Extrudate particles are rounded and can be optional be coated.
  • at the extrusion follows the following process conditions: Temperature at intake and nozzle each 50 ° C; Print: 30 bar, torque: 37 Nm; Screw speed: 100 revolutions per Minute.
  • Example 7
  • Preparation of inventive liquid detergent formulations
  • A liquid heavy-duty detergent of the following composition is produced, in each case based on the active substance content: Amount [wt%] ingredient 16.5 Linear alkylbenzenesulfonate (LAS, Cognis, Dusseldorf) 10 C 12 -C 18 fatty alcohol polyglycol ethers with 7 EO (Dehydol LT 7, Cognis) 1 Kaliumtrisphosphonmethylimin oxide (Sequion 10 H 60 ®; Fa. Polygon Chemie, Olten, Switzerland) 3 sodium citrate 8th sodium sulphate 3 Phthalimidoperoxyhexanoic acid (PAP) as granules (400-1200 microns; commercial product Eureco ® W; Solvay Solexis;. Bussi, Italy) 3.5 Inventive enzyme granules from example 6 0.25 Xanthan gum; Commercial product TGCS; Fa. Jungbunzlauer Xanthan, Pernhofen, Austria) 1 Perfume 0.1 Silicone antifoam (commercial product DC 2-3910, Wacker-Chemie, Munich) ad 100 water
  • The Made by placing the water in a stirred tank submitted and added to the xanthan. After swelling of xanthan (about 30 minutes), the sulfate is added. After that takes place the addition of the surfactants and other raw materials with stirring. The pH is adjusted to 5.0 ± 0.2 with concentrated NaOH set.
  • Example 8
  • comparison formulation
  • It enzyme granules were prepared as in Example 5, however with the difference that instead of the antioxidant equipped Aluminum oxide particles were used, the unmodified particles (Granules V1).
  • Example 9
  • Assessment of storage stabilities the proteases and the bleaching agent in the according to the examples 7 and 8 prepared recipes
  • The Liquid detergent formulation according to the invention from Example 7 with the enzyme particles according to the invention E1 from Example 6, the antioxidant of the invention from Example 5 was stored at 25 ° C. For comparison, the same liquid formulation with the enzyme particles Stored in V1. After periods of 0, 1, 2, 4 and 8 weeks The enzyme activity was determined by means of a "Continuous Flow apparatus "(company Skalar / Erkelenz) determined on the cleavage of casein, staining of the hydrolysis products with trinitrobenzene sulfonic acid and its photometric Determination.
  • in principle would be another established method in the art have been applicable to the determination of a protease activity. It was observed in the detergent according to the invention a significantly improved storage stability of the enzyme. At the same time, the storage stability of the bleaching agent decreased not essential.
  • This proves that this is compounded with the enzyme and immobilized Antioxidant the enzyme as the oxidation-sensitive ingredient effectively protects against inactivation. At the same time the localization ensures of the antioxidant for this, an interaction of the antioxidant takes place with the bleaching agent only to a slight extent, so that too, this is not essential during storage reacted.
  • Example 10
  • Preparation of further immobilized antioxidants
  • According to Example 5 further immobilized antioxidants were prepared with Disperal P3 as a carrier material according to the following procedure: antioxidant solvent reaction conditions achieved occupancy rate [weight%] L-ascorbic acid dimethylformamide 7 h, reflux 24.7 L-ascorbic acid dimethylformamide 3 days, room temperature 13.7 gallic acid water 3 h, reflux 21.8 DL-α-tocopherol tetrahydrofuran 3 days, room temperature 6.06 DL-α-tocopherol tetrahydrofuran 2 h, reflux 7.17 2-tert-butyl-4-methoxyphenol dioxane 3 h, reflux 7.4
  • Further Experiments in which Hybrane P / S 60 with gallic acid or 3,4,5-trimethoxybenzoic acid were also provided positive results.
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.
  • Cited patent literature
    • WO 00/27978 A1 [0003]
    • - EP 0290223 [0004]
    • WO 97/40128 [0016]
    • WO 00/29534 [0017, 0017]
    • WO 01/23513 [0018, 0018]
    • WO 91/02792 A1 [0042]
    • WO 92/21760 A1 [0042]
    • WO 95/23221 A1 [0042]
    • WO 02/088340 A2 [0042]
    • WO 03/038082 A2 [0042]
    • WO 03/054185 A1 [0042]
    • WO 03/056017 A2 [0042]
    • WO 03/055974 A2 [0042]
    • WO 03/054184 A1 [0042]
    • WO 02/10356 A2 [0045]
    • WO 02/44350 A2 [0045]
    • WO 03/002711 A2 [0045]
    • WO 03/054177 A2 [0045]
    • - DE 10138753 A1 [0045]
    • WO 96/29397 A1 [0049]
    • WO 98/12307 A1 [0049]
    • WO 97/14804 A1 [0049]
    • WO 96/34092 A2 [0049]
    • WO 99/06573 A1 [0050]
    • WO 98/45398 A1 [0051]
    • WO 2004/058955 A2 [0051]
    • WO 2004/058961 A1 [0051]
    • - EP 2005/006178 [0051]
    • WO 2005/056782 A2 [0051]
    • WO 2005/124012 A1 [0052]
    • WO 96/05284 A1 [0059]
    • WO 99/28430 A1 [0059]
  • Cited non-patent literature
    • Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 [0041]

Claims (18)

  1. An enzyme preparation in granule form, containing one or more enzymatically active proteins and, if desired, adsorbents, granulating aids and / or coating agents, characterized in that, moreover, an effective amount of a carrier-bound antioxidant is contained.
  2. Enzyme preparation according to claim 1, characterized in that the antioxidant is selected from the group phenolic or polyphenolic compounds, tocopherol, ascorbic acid, Mono or polyhydroxybenzoic acid, their salts and / or low molecular weight esters.
  3. An enzyme preparation according to claims 1 or 2, characterized in that it is the antioxidant gallic acid, trimethoxybenzoic acid, 4-hydroxybenzoic acid and / or their salts or esters.
  4. Enzyme preparation according to one of the claims 1 to 3, characterized in that the carrier is an organic Polymer is and the antioxidant covalently as a side chain is bound to the organic polymer.
  5. Enzyme preparation according to one of the claims 1 to 4, characterized in that the carrier is an organic Polymer is the antioxidant as a chain constituent contains.
  6. Enzyme preparation according to claim 5, characterized in that that the organic polymer is hydroxyl-containing Polymers, in particular hydroxyalkyl acrylates, hydroxyalkyl methacrylates, polyvinyl alcohol and / or their copolymers.
  7. Enzyme preparation according to claim 4, characterized in that that the organic polymer is an optionally substituted Polysaccharide acts.
  8. Enzyme preparation according to claim 4, characterized in that that the organic polymer is a polyester, a Polyesteramide or a polyurethane having hydroxyl or carboxylic acid end groups.
  9. Enzyme preparation according to claim 4, characterized in that that the organic polymer is a carboxyl group-carrying Polymer, in particular polyacrylic acid, polymethacrylic acid and or their copolymers.
  10. Enzyme preparation according to claims 1 to 3, characterized in that the antioxidant to a solid, substantially insoluble oxidic inorganic Connection is bound.
  11. Enzyme preparation according to one of the claims 1 to 3 and 10, characterized in that the antioxidant to a carrier selected from the group of silicic acid, Alumina, alumina hydroxide, zinc oxide, titanium dioxide bonded is, this carrier at least predominantly as particles in the nanoscale pond size range is present.
  12. Enzyme preparation according to one of the claims 1 to 11, characterized in that enzymes, proteases, amylases, CGTases, lipases, hemicellulases, in particular β-glucanase or mannanase, cellulases, in particular endoglucanase, cellobiohydrolase, Oxidoreductase, choline oxidases or perhydrolases are present.
  13. Enzyme preparation according to claims 1 to 12, characterized in that as adsorbent starch, Cereal flour, sodium sulfate, sodium citrate, salts, aluminosilicate (Zeolite), organic polymers or the like are included.
  14. Esters of gallic acid, trimethoxybenzoic acid, of 4-hydroxybenzoic acid and / or salicylic acid with hydroxyl-containing organic polymers for use as a carrier-bound antioxidant.
  15. Process for the preparation of enzyme preparations containing carrier-bound antioxidants, characterized in that the enzymes obtained from fermenter broths are added in dried or dissolved form to an adsorbent and, if desired, under drying conditions to a granule optionally subjecting the granules thus contained to one or more coating processes, wherein the carrier-bound antioxidants according to the invention are added before or after the granulation step and / or before or after the coating step.
  16. A surfactant-containing preparation containing simultaneously a bleaching agent and an enzyme granules in liquid matrix.
  17. Surfactant-containing preparation according to claim 16, characterized characterized in that the liquid matrix predominantly consists of surfactants and is substantially anhydrous.
  18. Surfactant-containing preparation according to the claims 16 or 17, characterized in that the bleaching agent is an organic Peracid, especially phthalimido-hexane percarboxylic acid contains.
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DE102014226251A1 (en) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Use of inorganic oxides, hydroxides or oxide hydroxides in enzyme-containing detergents or cleaners to increase the stability of enzymes

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