WO1994023005A1 - Enzyme composition for washing and cleaning agents - Google Patents

Enzyme composition for washing and cleaning agents Download PDF

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Publication number
WO1994023005A1
WO1994023005A1 PCT/EP1994/000934 EP9400934W WO9423005A1 WO 1994023005 A1 WO1994023005 A1 WO 1994023005A1 EP 9400934 W EP9400934 W EP 9400934W WO 9423005 A1 WO9423005 A1 WO 9423005A1
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Prior art keywords
wt
enzyme
granules
characterized
mm
Prior art date
Application number
PCT/EP1994/000934
Other languages
German (de)
French (fr)
Inventor
Kathleen Paatz
Wilfried Rähse
Werner Pichler
Udo Sturm
Horst Upadek
Original Assignee
Cognis Gesellschaft Für Biotechnologie Mbh
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND 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

Abstract

In order to improve the solubility, to increase the storage stability and to reduce enzyme activity losses during production of enzyme granulates suitable to be incorporated into washing or cleaning agents and containing an enzyme and an organic and/or inorganic carrier, a granulation-auxiliary system is used which consists of alkali-carboxymethylcellulose with substitution degrees from 0.5 to 1 and of polyethylene glycol and/or alkyl- or alkenylpolyethoxylate. When more than 2 % by weight alkali-carboxymethylcellulose are contained in the granulates, they contain at least 0.5 % by weight polyethylene glycol with less than 1000 mean molar mass and/or alkyl- or alkenylpolyethoxylate with at least 20 ethoxy groups. The new enzyme granulates have such a high speed of decomposition that when they are used in washing agents the wash bath contains enough enzyme to remove enzymatically removable soil already in the initial phase of machine washing.

Description

"EnzvmzubereitunQ for washing and cleaning agents"

The invention relates to an enzyme granule, a process for its Herstel¬ lung and the use of the granules in solid washing and cleaning preparations.

Enzymes, particularly proteases, are widely used in detergents, washing aids, and cleansers. Usually, the enzymes are not used as concentrates, but in mixtures with a diluent and carrier material used. By mixing with such enzyme preparations usual detergents, so during storage a substantial reduction in Enzymak¬ tivity may occur, particularly when bleaching-active compounds are present. The application of enzymes on carrier salts with simultaneous Gra¬ nulation according to the German Offenlegungsschrift DT 1617 190 as beziehungs¬ by gluing with nonionic surfactants according to the German Of¬ fenlegungsschrift DT 16 17 118 or aqueous solutions of cellulose ethers according to the German Offenlegungsschrift DT 1767568 does not lead to a significant improvement in storage stability because the sensitive enzymes are in such Aufmischungen usually on the surface of Trä¬ gersubstanz. Although the storage stability of the enzymes may be increased substantially if one coats the enzymes with the carrier material be¬ relationship as embedded in it and then sen by extrusion, Pres¬ and transferred Marumerisieren in the desired particle shape, such as, for example, in German patent publication DE 16 17232 , German Offen¬ legungsschrift DT 2032 768 and German Auslegeschriften described DE 21 37042 and DE 21 37,043th However, such enzyme preparations have unsatisfactory solubility. The undissolved particles may get caught in the clothes items and contaminate it or they are unused transferred to the waste water. The German Offen¬ DT legungsschrift 1803099 encapsulating compositions known that mixed solid of a Ge acids or acidic salts and carbonates as beziehungs¬ consist bicarbonates and which disintegrate on addition of water, improve Although the dissolving power, they are extremely sensitive to moisture and therefore require additional protective measures.

Another drawback of the above preparation is the fact that the enzymes can be processed only in the form of dry powder. The commonly encountered in the enzyme producing fermentation broths can be in this form, not use, but must first be drained. Also such methods are bound to this requirement, where only easily soluble carrier materials such as sugar, starch and cellulose ethers are used as binders for the production of enzyme preparations.

From the European patent specification EP 168526 enzyme granules are known which include water-swellable starch, zeolite, and water-soluble Granulier¬ tool. In this document a method for manufacturing such formulations is proposed which is substantially be¬ therein, thiocyanate, concentrating a fermenter solution freed from insoluble constituents, at staggered with said additives and granulating the resulting mixture. The process with the vorgeschla¬ there antigenic aggregate mixture is advantageously carried out with fermentation solutions which beispiels¬, to a relatively high dry matter content were 55 wt .-%, concentrated. In addition, the granules thus produced have a high dissolving speed or Zerfalls¬ under washing conditions that the granules already partially disintegrate relatively rapidly in storage and the enzymes are deactivated.

From the international patent application WO 92/11347 describes enzyme granules for use in granular detergents and cleaning agents are known, the weight 2 wt .-% to 20 wt .-% enzyme, 10 wt .-% to 50 wt .-% swellable starch, 5 contain .-% to 50 wt .-% of water-soluble organic polymer as Granulierhilfsmit¬ tel, 10 wt .-% to 35 wt .-% of cereal flour and 3 wt .-% to 12 wt .-% Was¬ ser. enzyme processing is possible without major losses in activity by such aggregates and also the storage stability of the enzymes in the granules is satisfactory. From this document it is also known that sodium carboxymethyl the disintegration and dis- reduces pergiergeschwindigkeit of the granules in cold wash liquors, while this effect can be changed in the direction to a higher rate of dissolution by the addition of higher molecular weight polyethylene glycol. However, the enzyme granules described therein do not always have such a high rate of disintegration that sufficient enzyme is when they are used in detergents already in the initial phase of machine laundry in the wash liquor available to remove dirt enzymatically removable An¬.

It was therefore the object, by a manufacturing method which allows the use of low concentrations of fermentation broths Pulverei¬ properties, better to ver¬ particular, the solubility of the known products, to increase the storage stability of both the enzymes and the these ent-retaining granules further and to reduce the loss of activity in the enzyme processing continues. This object is solved by the invention as hereinafter described essentially by a special granulation auxiliary system containing be¬ relationship as dust-binding component and a solubilizing component körnverfestigende in optimized conditions.

The invention relates to a material suitable for incorporation in particular particle-shaped washing or cleaning agent Enzyme granules containing enzyme and inorganic and / or organic carrier material and carboxy- methyl cellulose containing granulation auxiliaries, which is characterized gekennzeich¬ net, that it contains a granulation aid of alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or alkyl- or Alkenylpolyethoxylat, with the proviso that, in each case based on the final granules, at least 0.5 wt .-% Poly ethylene glycol having an average molecular weight below 1,000 and / or alkyl relationship be¬ Alkenylpolyethoxylat as having at least 20 ethoxy groups vor¬ hands is, if more than 2 wt .-% is contained alkali metal carboxymethyl cellulose.

Under the degree of substitution of carboxymethylcellulose is the number of etherified, a carboxy ethyl group bearing Sauerstoffato e per Saccharomyces chloride monomer to understand the cellulose. The degree of substitution with carboxymethyl preference as used is in the range of 0.8 to 0.95, there can be obtained particularly firm granules when they are used or lower amounts are required to errichen a certain Gra¬ nulatfestigkeit, than with the use of cellulose with lower degree of substitution. Thus Garnulatfestigkeiten for example, by the presence of sodium carboxymethylcellulose with degree of substitution 0.85 to 0.95 even at amounts of 1 wt .-%, based on granules in the granulation auxiliary system, are achieved, which of those when using the twice the amount of sodium carboxymethylcellulose degree of substitution 0.65 to 0.75, respectively. In addition, a higher throughput can er¬ through the extruder by the use of said highly substituted carboxymethylcellulose in the production of granulocytes late in the extrusion step is sufficient.

The enzyme granules in a preferred embodiment, 1 wt .-% to 30 wt .-%, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70 wt .-% to 94 wt .-% inorganic and / or orga African carrier material and 5 wt .-% to 50 wt .-% carboxymethylcellulose containing granulation as well as the balance to 100 wt .-% water.

As a granulation aid of an inventive enzyme granulate preferably contains a mixture comprising, based on the final granulocytes lat, 0.1 wt .-% to 10 wt .-%, particularly 0.5 wt .-% to 5 wt .-% Car¬ boxymethylcellulose and 0.1 wt .-% to 10 wt .-%, particularly 0.5 wt .-% to 4 wt .-% polyethylene glycol having an average molecular weight of 200 to 600 and / or a Polyethoxylats according to formula (I),

R- (0CH 2 CH) n -0H (I)

R men a linear or branched alkyl or alkenyl radical having up to 3 CC double bonds containing 10 to 22, in particular 16 to 18 C-Ato and the average degree of ethoxylation n is a number from 20 to 80, more particularly 30 to 45 sondere means.

Furthermore, the invention relates to a method for producing a der¬-like enzyme granulate with a grain size of 0.1 mm to 2 mrc by ex trudieren a by mixing a liberated by microfiltration of unlös¬ union ingredients, concentrated fermentation broth with the carrier material and the granulation aid as aggregates ent standenen enzyme premix commanding device spheronizing the extrudate in a Ron-, drying and optionally applying a dye or pigment-containing coating, characterized in that the Fermen¬ one tationsbrühe with an additive is mixed, the solvent system a Granulierhilfs¬ from alkali carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate, with the proviso that, in each case based on the final granules, at least 0.5 wt .-% polyethylene glycol having an average molecular weight below 1,000 and / or alkyl or Alkeny lpolyethoxylat be used with at least 20 ethoxy groups, when more than 2 wt .-% cellulose alkali Carboxymethyl¬ is included in the granulation auxiliary.

Suitable enzymes are primarily derived from microorganisms such as bacteria or fungi, proteases, lipases, amylases and / or cellulases are suitable, wherein produced by species of Bacillus proteases as well as their mixtures are preferred lipases. They are in a known manner tion processes obtained from suitable microorganisms, for example, in the German patents DE 1940488, DE 2044 161, DE 2201 803 and DE 21 21 397, the US patents US 3 632 957 and US 4 264 738 by Fermenta¬ and European Patent application EP described 006,638th Particularly advantageously, the erfindungsge¬ Permitted process for formulation of highly active proteases of the so-called second and higher generations can be used, including, for example, Savinase (R) and from the international patent application WO 91/2792 are known enzymes, their stable incorporation in detergents and Reinigungs¬ medium often causes problems. According to the invention it is possible to use the products resulting from the fermentation processes broths of extracellular enzymes by Ab¬ separating the insoluble impurities by microfiltration and nachfol¬ constricting concentration by ultrafiltration and optionally an¬ closing evaporation in vacuum to be converted into storage-stable, weitge¬ starting odorless granules directly. The formation of undesirable En¬ zymstäube and Akti¬ occurring in additional drying processes vitätsverluste be avoided. Enzymes are preferably included in the inventive granules in amounts of 4 wt .-% to 20 wt .-%. If it is in the inventive enzyme granules to a protease-containing formulation, the protease activity is preferably 150,000 protease units (PU, as determined by the (in Tenside 2, 1970), method described 125) to 350,000 PE, in particular 160000 PE to 300,000 PE, per gram of enzyme granules ,

As support materials, all organic or inorganic powdery substances are in principle usable, which enzymes to be granulated does not destroy or only negligibly, or deactivate, and are stable under granulation. Such substances include spielsweise starch, cereal flour, cellulose powder, alkali metal alumosilicate, more particularly zeolite, layer silicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example Al kalichlorid, alkali sulfate, alkali carbonate or alkali metal acetate, with sodium or potassium, the preferred alkali metals are. a Träger¬ is preferably made of water-swellable starch, corn meal and cellulose powder used gege¬ appropriate, as well as alkali metal carbonate material mixture.

In the water-swellable starch, it is preferably Mais¬ starch, rice starch, potato starch or mixtures of these, the use of corn starch is particularly preferred. Swellable starch is preferably contained in the inventive enzyme granules in amounts of 20 wt .-% to 50 wt .-%, particularly from 25 wt .-% to 45 wt .-%. The sum of the quantities of swellable starch and flour is vorzugs¬ not, over 80 wt .-%, in particular 32 wt .-% to 65 wt .-%.

In the inventively suitable cereal flour is insbeson dere a producible from wheat, rye, barley or oats product or a mixture of these flours, whole grain flours are preferred. Un¬ ter a whole grain flour is understood to mean a non-fully ausge¬-ground flour in the invention, which has been prepared from whole, unhusked grain or at least mainly consists of such a product, the remainder consisting of fully ground flour or starch. Preferably Commercial wheat flours, such as Type 450 or Type 550 used. The use of flour products of leading to abovementioned swellable starches cereals is possible if care is taken that the flour made from whole grains. Due to the flour component of the aggregate material mixture, a significant reduction in odor of the enzyme preparation is be¬ can purportedly ranges er¬ which exceeds the odor reduction by incorporating equal amounts of corresponding types of starch by far. Such Ge is preferably contained in the inventive enzyme granules in amounts of from 10 wt .-% to 35 wt .-%, particularly from 15 wt to 25 wt .-% treidemehl.

The enzyme granules of the invention preferably contain 1 wt .-% to 50 wt .-%, preferably 5 wt .-% to 25 wt .-% of Granulierhilfsmittel¬ systems, alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or contains alkyl polyethoxylate. This granulation preferably, based on the final enzyme granules, 0.5 wt .-% to 10 wt .-%, particularly 0.5 wt .-% to 5 wt .-% alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 5 wt .-%, particularly 0.5 wt .-% to 3 wt .-% Polyethylen¬ glycol and / or alkyl polyethoxylate containing it being important that min¬ least 0.5 wt .-%, in particular 0.8 wt .-% is present to 2 wt .-% polyethylene glycol having an average molecular weight below 1,000 and / or alkyl polyethoxylate containing at least 20 ethoxy groups, when more than 2 wt .-% is contained alkali carboxymethylcellulose. Highly substituted Carboxymethyl¬ cellulose with degrees of substitution of up to 3, is preferably not included in the inventive granulation auxiliary. Carboxymethyl celluloses with degrees of substitution below 0.5 are in the inventive granulation auxiliary system is also preferably not included.

Optionally, as additional components of the Granulierhilfsmit¬ telsystems also cellulose or starch ethers such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatine, casein, tragacanth, coloring todextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers or polymers are used natür¬ or synthetic origin. Useful ground synthetic water-soluble polymers are polyacrylates, polymethacrylates, Copo- mers of acrylic acid with maleic acid or vinyl group-containing compounds Verbin¬, further polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone. As far as in the above-mentioned compounds to sol¬ che with free carboxyl groups, they are normally present in the form of their alkali metal salts, in particular their sodium salts. Such zusätz¬ Liche granulation can in the inventive enzyme granules in amounts up to 10 wt .-%, particularly from 0.5 wt .-% to 8 wt .-% his hold ent. Higher molecular weight polyethylene glycols, i.e., those having an average molecular weight above 1,000, may be used as synthetic wasser¬ soluble polymers having dust-binding effect, but cause ge rade the higher molecular weight polyethylene glycols surprisingly un¬ desirable increase of the required granulate dissolution time, so that punch these Sub¬ preferably completely absent in the novel enzyme granules.

To produce the enzyme granules according to the invention are preferably produced from fermentation broths which are freed by microfiltration of insoluble accompanying substances. The microfiltration is preferably carried out as crossflow microfiltration using porous tubes with micro pores greater than 0.1 μ, flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 performed bar, such as in the European patent application EP 200,032th The microfiltration is vor¬ preferably by ultrafiltration, optionally evaporation followed by vacuum, concentrated. out the concentration can, as described in International Patent Application WO 92/11347, so the wer¬ that only relatively low dry matter contents of preferably 5 wt .-% vor¬ to 50 wt .-%, in particular 10 wt .-% wt .-% passes to 40 wt. If the protease-containing fermentation broths are used be¬ the protease content in particular 600000 PE / g carries at this stage of the concentrate preferably 500,000 PE / g to 1 500 000 PE / g to 1 000000 PE / g. The concentrate is conveniently a previously prepared dry, powdered to granular mixture of the above-described metered Zu¬ impact materials. The water content of the mixture should be chosen so that it can be converted in the processing with stirring and beating tools into granular, non-sticky at room temperature and the particles plastically deform upon application of higher pressures and can extrude.

The free-flowing premix is ​​then processed in principle known manner in a kneader and an adjoining extruder to form a plastic mass, as a result of the mechanical processing, the mass to temperatures between 40 ° C and 60 ° C, in particular 45 ° C to 55 ° C may become warm. The material leaving the extruder will be good by a Lochschei¬ out with subsequent cutting blade and thereby comminuted into cylinder-shaped particles of a defined size. Advantageously, the diameter of the holes in the perforated disc is 0.7 mm to 1.6 mm, preferred wise 0.8 mm to 1.2 mm. The present in this form may then be dried and later use are supplied. However, it has proved advantageous that subsequently to spheronize the extruder and chopper cylindrical particles leaving, that is to round them off in suitable equipment and deburring. Such spheronizing is considering regulations for example in the German Aus¬ DE 2137042 and DE 2137043 described. a device ary of a cylindrical container with statio¬ consist plate fixed side walls and a bottom side friction-rotatably mounted thereto is used. Devices of this type are available under the tradename Marumerizer (R) in the art spreads. ^

After the spheronization the still moist beads are continuously or batchwise, preferably dry system by using a fluidized-bed, at preferably 35 ° C to 50 ° C and particularly at a maximum product temperature of 45 ° C, to a residual moisture content of 4 wt .-% to 10 wt .-%, preferably 5 wt .- dried% to 8 wt .-%. After or preferably during the drying coating agents and coating the particles can additionally be introduced. Suitable Hüll¬ materials are in particular the film-forming agent under the aforementioned wasser¬ soluble organic polymers. Furthermore, can be at this stage, dyes or pigments applied to the particles in order to cover über¬ as a possible intrinsic color, which usually originates from the enzyme concentrate or to change. As the inert and physiologically-pending unbe¬ thinking pigment, in particular titanium dioxide has proven that preferential example in aqueous dispersion is introduced. The water immersion on the Pigmentdisper¬ or supplied via the polymer solution is at the same time made or subsequently required drying again removed.

The enzyme granules is preferably used for the production of solid, more particularly particulate detergents or cleaning agents which may be obtained by ein¬ multiple mixing the enzyme granulates with customary in such compositions further powder components. For incorporation in particulate detergents and cleaners, the enzyme granules preferably vor¬ average grain sizes in the range of 0.1 mm to 2 mm, in particular from 0.4 mm to 1.6 πrni on.

By sieving or air classification auftre¬ tend dust-like components, in the production, possibly with a grain size below 0.1 mm, in particular less than 0.4 mm and any coarse fractions with a particle size above 2 mm, in particular more than 1.6 mm away, and optionally in the manufacturing process are recycled. The granules of the invention preferably contain less than 5 wt .-%, particularly at most 1 wt .-% of Par¬ tikeln with grain sizes outside the range of 0.2 mm to 1.6 mm.

In a preferred embodiment of the inventive method the wer¬ 10 wt .-% to 50 wt .-% of the concentrated fermentation broth with 70 wt .-% to 90 wt .-% of the carrier material and 0.5 wt .-% to 10 degrees. - mixed% of the granulation. The carrier material contains vor¬ preferably 10 wt .-% to 70 wt .-% of cereal flour, 10 wt .-% to 70 wt .-% water-swellable starch, 3 wt .-% to 10 wt .-% of sucrose and up to 10 wt .-% cellulose powder, based on the final enzyme granules.

The enzyme preparation obtained consists of substantially rounded, staub¬ free particles having a bulk density of about 500 to 900 grams per liter, in particular 650 to 880 grams per liter in the rule. Their enzyme activity can, due to the flexible Trockensubstanzge¬ stop the brewing before mixing with the additives, with the use of protease-containing Fer enter brew to values ​​in the range of preferred wise from 150,000 to 350,000 protease units per gram (PU / g), particularly 160000 PE / g to 300,000 PU / g is adjusted. The granules of the invention are characterized by a very high storage stability, especially at temperatures above room temperature and high humidity, as well as a rapid solubility behavior in the wash liquor. Preferably granules of the invention set 100% of their enzyme activity released within 3 Mi¬ grooves, in particular within 90 seconds to 2 minutes in water at 25 ° C.

Examples

example 1

By fermentation of the method described in the international patent application WO 91/2792 method by transformation of a gene sequence of Bacillus lentus DSM 5483 modif ed Bacillus licheniformis is (ATCC 53926) analogously to the ange¬ added method in the German patent specification DE 2,925,427 was obtained a biomass-containing fermentation broth which contained about 65,000 protease units per gram (PU / g). This was purified by decantation, crossflow microfiltration, Ultrafiltation (separation limit at molecular weight 10,000), followed by evaporation in vacuo by the method described in International Patent Application WO 92/11347 approach to a protease content of 700,000 PE / g concentrated (Bl). The so-up concentrated fermentation broth was mixed in a flask equipped with ver¬ rotary impact tool with the mixer shown in Table 1 pictures and homogenized in a kneader provided with an external cooling. The extrusion of the plastic composition was carried out by means of a disk with a Loch¬ (hole diameter 0.9 mm) and a rotating knife ausgerüste¬ th extruder. the characterized in Table 1 by their composition extrudates XI to obtain X4, and X5 and X6, in which a disc-Loch¬ was used with hole diameter 1.2 mm, according to the dung Erfin and comparing extrudates VI to V3, respectively lengths of 0.7 mm to 1 mm, in a spheronising device (Marumerizer (R)) during a processing time of about 1 minute while simultaneously dusting with powdered calcium carbonate (3 wt .-%) have been deformed to rounded particles and deburred. The material leaving the spheronizer Good was dried in a fluidized bed dryer at temperatures from 40 ° C to 45 ° C inner¬ semi 15 minutes to a water content of 6 wt .-%. By subsequent sieving particles having particle sizes below 0.4 mm and more than 1.6 substantially removed, which have been fed to the process at the stage of mixing comparison with the aggregates again were. The late Enzymgranu¬ were coated by spraying an aqueous titanium dioxide pigment suspension during the fluidized-bed drying. This gave the erfindungs¬ proper enzyme granules Pl to P6 respectively for comparison, the granulocytes late VG 1 to VG 3 to those given in Table 2 release times. Table 1 Composition of extrudates [wt .-%]

XI X2 X3 X4 X5 X6 VI V2 V3

Bl 34 32 32 32 32 32 32 32 32

Cellulose powders a) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5

Sucrose 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5

Wheat flour T 450 19 19 19 19 17 19 19 16 15

Corn Starch 37 38 39 36 38 38 35 33 33

CMC-lb) 2 2 - 3 4 - 6 10 10 I

CMC II C) - - 1 - - 2 - - - <→

PEG-I d) - 1 - 2 1 1 - - -

Surfactant e) - - 1 - - - - - -

PEG-Ilf) - - - - - - 1 2

"

a): Technocel (R) 30 (manufactured cellulose filler factory) b): Carbocel (R) 300 (degree of substitution 0.65-0.75; manufacturer Lamberti CMC) c): Carbocel (R) 500 (degree of substitution 0.85 0.95; manufacturer Lamberti CMC) d): polyethylene glycol, average molecular weight 400 e): 40-fold ethoxylated tallow fatty alcohol (manufactured by Henkel) f): polyethylene glycol, average molecular weight 2,000

14

example 2

The determination of the dissolution time was carried out in a measuring apparatus comprising a temperature-controlled, double-walled beaker, an inclined blade stirrer, trodes a temperature sensor and a conductivity of 4 Elek¬, which the conductivity meter (Type LF 537, Fa. WTW) with a xt- Schreiber is connected. In the beaker 500 ml of water were heated with stirring to 20 ° C. At constant temperature, 5.0 g of the enzyme granules was stirred and added the conductivity curve with the time recorder. The time in which 90% of the final value is reached (after 15 minutes), equivalent to the dissolution time in Table 2 below.

The inventive enzyme granules from Example 1 dissolved in times of less than 2 minutes completely, while the getesten for comparison granules required much longer periods. It is noteworthy that the increase in the proportion of higher molecular weight polyethylene glycol (granulate VG3 in comparatively to VG2) resulted in a slowing of the dissolution.

Table 2: dissolution time of the enzyme granules

Enzymgra¬ granulate dissolution time [Min.Sek]

pl 1.40

P2 1.22

P3 1.56

P4 1.48

P5 1.58

P6 1.45

VG1 4.48

VG2 4.16

VG 3 5.30

Claims

claims
1. containing enzyme and inorganic and / or organic Trä¬ granules for incorporation in detergents or cleaning agents suitable Enzym¬, germaterial carboxymethylcellulosehaltiges and granulation, characterized in that it contains a granulation aid from Al¬ kali carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or alkyl- or Alkenylpolyethoxylat, with the proviso that, in each case based on the final granules, at least 0.5 wt .-% available polyethylene glycol having an average molecular weight below 1,000 and / or alkyl or Alkenylpolyethoxylat having at least 20 ethoxy groups is, if more than 2 wt .-% is contained Al¬ kali carboxymethylcellulose.
2. Enzyme granules as claimed in claim 1, characterized in that 1 wt .-% to 30 wt .-%, calculated as dry substance, protease, lipase, Amylä¬ se and / or cellulase, 70 wt .-% to 94 wt contains% inorganic and / or organic carrier material and 5 wt .-% to 50 wt .-% cellulosic carboxymethyl¬ granulation as well as the balance to 100 wt .-% water.
3. Enzyme granules as claimed in claim 1 or 2, characterized in that it contains as granulation aid a mixture containing, in each case bezo¬ gene on the final granules, 0.1 wt .-% to 10 wt .-%, particularly 0.5 wt % to 5 wt .-% carboxymethylcellulose, and 0.1 wt .-% to 10 wt .-%, particularly 0.5 wt .-% to 4 wt .-% polyethylene glycol having an average molecular weight of 200 to 600 and / or a Polyethoxylats according to formula (I),
R- (0CH 2 CH 2) n-0H (I)
in which R is a linear or branched alkyl or alkenyl group containing up to 3 CC double bonds containing 10 to 22 carbon atoms and the mitt¬ sized degree of ethoxylation n is a number from 20 to 80 means contains.
4. Enzyme granules as claimed in any of claims 1 to 3, characterized gekennzeich¬ net, that the carrier material, based on enzyme granules, 20 wt .-% to
• 50 wt .-%, in particular 25 wt .-% to 45 wt .-% water-swellable starch, especially corn starch containing.
5. Enzyme granules as claimed in any of claims 1 to 4, characterized gekennzeich¬ net, that the carrier material, based on enzyme granules, 10 wt .-% to 35 wt .-%, in particular 15 wt .-% to 25 wt .-% of cereal flour, insbe¬ sondere wheat flour, rye flour, barley flour, oat flour and its Ge mix, up to 10 wt .-%, especially 2 wt .-% to 6 wt .-% Cellulo¬ se, layer silicate, alkali metal carbonate, alkali metal chloride, alkali metal sulfate and / or alkali metal containing and / or the granulation aid additionally contains up to 10 wt .-%, particularly 0.5 wt .-% to 8 wt .-% of water-soluble or dispersible oligomers or polymers of natural or synthetic origin.
6. Enzyme granules as claimed in any of claims 1 to 5, characterized gekennzeich¬ net, that it keeps protease with an activity of 150,000 to 350,000 PE PE, in particular 160000 to 300000 PE PE per gram of enzyme granules ent.
7. Enzyme granules as claimed in any of claims 1 to 6, characterized gekennzeich¬ net, that it has an average particle size of 0.1 to 2 mm, in particular from 0.4 to 1.6 mm and less than 5 wt .-%, in particular at most 1 wt .-% comprises of particles with particle sizes outside the range of 0.2 mm to 1.6 mm.
8. Enzyme granules according to one of claims 1 to 7, characterized gekennzeich¬ net, that within 3 minutes, in particular within 90 seconds to 2 minutes, releasing in water at 25 ° C 100% of its Enzymaktivitä.
9. A process for preparing a composition suitable for incorporation into detergent or detergent enzyme granules with a particle size of 0.1 mm to 2 mm by extruding a centerless fermentation broth by mixing a liberated by micro filtration of insoluble constituents, aufkonzen- with the carrier material and the granulation ¬ tool formed as aggregates enzyme premix, Sphaerotheca ronisierung the extrudate in a spheronizer, drying and gege¬ appropriate, applying a dye or pigment containing Über¬ train, characterized in that admixing the fermentation broth with an additive comprising a granulation auxiliary system of Alka li ¬ carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate, with the proviso that, in each case based on the final granules, at least 0.5 wt .-% polyvinyl lyethylenglykol having an average molecular weight below 1,000 and / or alkyl- Al¬ b eziehungsweise Alkenylpolyethoxylat having at least 20 ethoxy groups are used where more than 2 wt .-% alkali Carboxymethyl¬ cellulose is included in the granulation auxiliary.
10. A method according to claim 9, characterized in that 10 wt .-% to 50 wt .-% of the concentrated fermentation broth with 70 wt .-% to 90 wt .-% of the carrier material and 0.5 wt .-% to 10 mixed wt .-% of the granulation auxiliary system.
11. The method of claim 9 or 10, characterized in that the carrier material, based on the final enzyme granules 10 wt .-% to 70 wt .-% of cereal flour, 10 wt .-% to 70 wt .-% in water quell¬ includes capable starch, 3 wt .-% to 10 wt .-% of sucrose and up to 10 wt .-% cellulose powder.
12. The method according to any one of claims 9 to 11, characterized in that one carries out the extrusion through a perforated plate whose holes have a diameter of 0.7 mm to 1.6 mm.
13. The method according to any one of claims 9 to 12, characterized in that, after spheronizing of the extrudate, the granules at Tempe¬ temperatures of 35 ° C to 50 ° C to a water content of 4 wt .-% to 10 wt .-% dries.
14. Use of enzyme granules to any one of claims 1 to 8 for preparing solid accordance restriction means particularly particulate detergents or Reini¬.
PCT/EP1994/000934 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents WO1994023005A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEP4310506.8 1993-03-31
DE19934310506 DE4310506A1 (en) 1993-03-31 1993-03-31 Enzyme preparation for washing and cleaning agents

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DE1994503879 DE59403879D1 (en) 1993-03-31 1994-03-23 Enzyme preparation for washing and cleaning products
EP19940912528 EP0692016B1 (en) 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents

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Cited By (39)

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WO1996016151A1 (en) * 1994-11-18 1996-05-30 Genencor International, Inc. Coated enzyme granules
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
US6075001A (en) * 1996-04-26 2000-06-13 Henkel Kommanditgesellschaft Aug Aktien Enol esters as bleach activators for detergents and cleaners
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
US6417151B1 (en) 1997-04-04 2002-07-09 Henkel Kommanditgesellschaft Auf Aktien Activators for peroxide compounds in detergents and cleaning agents
US6417152B1 (en) 1997-07-30 2002-07-09 Henkel Kommanditgesellshaft Auf Aktien Detergent containing glucanase
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US6703357B1 (en) 1997-07-30 2004-03-09 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent for hard surfaces, containing glucanase
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6875734B2 (en) 2003-02-03 2005-04-05 Clariant Gmbh Use of transition metal complexes as bleach catalysts
US7015185B2 (en) 2002-03-15 2006-03-21 Clariant Gmbh Ammonium nitriles and the use thereof as hydrophobic bleaching activators
EP1754781A1 (en) 2005-08-19 2007-02-21 The Procter and Gamble Company A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology
US7300782B2 (en) 2001-12-21 2007-11-27 B.R.A.I.N. Biotechnology Research And Information Network Ag Glycosyl hydrolases
EP0917430B2 (en) 1996-05-13 2008-03-12 Biovet JSC Enzyme pre-granules for granular fodder
DE102007016391A1 (en) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor
DE102007028310A1 (en) 2007-06-20 2008-12-24 Clariant International Ltd. Surfactant mixtures with synergistic properties
EP2088186A1 (en) 2003-12-13 2009-08-12 Henkel AG & Co. KGaA Multi-component thin-to-thick system
DE102008013606A1 (en) 2008-03-11 2009-09-17 Clariant International Ltd. A process for the preparation of solid alkaline earth metal secondary paraffinsulfonic
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
DE102011010818A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd. Use of transition metal complexes as bleach catalysts in laundry detergents and cleaning products
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
DE102014009836A1 (en) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Sodium salts of secondary alkane sulfonates containing compounds, their preparation and use as well as washing, disinfection and cleaning compositions comprising these
EP2302025B1 (en) 2009-09-08 2016-04-13 The Procter and Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (en) 2015-12-01 2017-06-07 Basf Se Bleach catalysts
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

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DE4420730A1 (en) * 1994-06-15 1995-12-21 Henkel Kgaa A process for deodorizing and stabilizing biotechnological value obtained substances and their aqueous preparations
DE19615776A1 (en) * 1996-04-20 1997-10-23 Henkel Kgaa Löslichkeitsverbessertes enzyme granulate
DE19651446A1 (en) 1996-12-11 1998-06-18 Henkel Kgaa Coated enzyme preparation with improved solubility

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JPS60168385A (en) * 1984-02-09 1985-08-31 Showa Denko Kk Granulation of enzyme
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See also references of EP0692016A1 *

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016151A1 (en) * 1994-11-18 1996-05-30 Genencor International, Inc. Coated enzyme granules
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
US5783542A (en) * 1995-07-27 1998-07-21 Diversey Lever, Inc. Anionic stabilized enzyme based clean-in-place system
US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6075001A (en) * 1996-04-26 2000-06-13 Henkel Kommanditgesellschaft Aug Aktien Enol esters as bleach activators for detergents and cleaners
EP0917430B2 (en) 1996-05-13 2008-03-12 Biovet JSC Enzyme pre-granules for granular fodder
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
US6417151B1 (en) 1997-04-04 2002-07-09 Henkel Kommanditgesellschaft Auf Aktien Activators for peroxide compounds in detergents and cleaning agents
US6703357B1 (en) 1997-07-30 2004-03-09 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent for hard surfaces, containing glucanase
US6417152B1 (en) 1997-07-30 2002-07-09 Henkel Kommanditgesellshaft Auf Aktien Detergent containing glucanase
US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US7300782B2 (en) 2001-12-21 2007-11-27 B.R.A.I.N. Biotechnology Research And Information Network Ag Glycosyl hydrolases
US7015185B2 (en) 2002-03-15 2006-03-21 Clariant Gmbh Ammonium nitriles and the use thereof as hydrophobic bleaching activators
US6875734B2 (en) 2003-02-03 2005-04-05 Clariant Gmbh Use of transition metal complexes as bleach catalysts
US7737103B2 (en) 2003-12-13 2010-06-15 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
EP2088186A1 (en) 2003-12-13 2009-08-12 Henkel AG & Co. KGaA Multi-component thin-to-thick system
US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
EP1754781A1 (en) 2005-08-19 2007-02-21 The Procter and Gamble Company A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US8785362B2 (en) 2005-08-19 2014-07-22 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
DE102007016391A1 (en) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor
DE102007028310A1 (en) 2007-06-20 2008-12-24 Clariant International Ltd. Surfactant mixtures with synergistic properties
US8426635B2 (en) 2008-03-11 2013-04-23 Clariant Finance (Bvi) Limited Process for preparing solid alkaline earth metal salts of secondary paraffinsulphonic acids
DE102008013606A1 (en) 2008-03-11 2009-09-17 Clariant International Ltd. A process for the preparation of solid alkaline earth metal secondary paraffinsulfonic
EP2302025B1 (en) 2009-09-08 2016-04-13 The Procter and Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
EP2805942A1 (en) 2010-12-13 2014-11-26 Basf Se Bleach catalysts
WO2012107187A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd Use of transition metal complexes as bleach catalysts in washing and cleaning compositions
DE102011010818A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd. Use of transition metal complexes as bleach catalysts in laundry detergents and cleaning products
DE102014009836A1 (en) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Sodium salts of secondary alkane sulfonates containing compounds, their preparation and use as well as washing, disinfection and cleaning compositions comprising these
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (en) 2015-12-01 2017-06-07 Basf Se Bleach catalysts
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

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DK692016T3 (en) grant
DE4310506A1 (en) 1994-10-06 application
DK0692016T3 (en) 1998-04-20 grant
EP0692016B1 (en) 1997-08-27 grant

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