Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38672—Granulated or coated enzymes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

• the invention encompasses an enzyme containing preparation containing at least one enzyme and a detergent containing such preparation.
• preparation means either a granulate or a liquid slurry.
• the slurry can be either anhydrous or substantially anhydrous, or it can be aqueous.
• enzyme containing preparations can be used in different fields, e.g. in the field comprising digestive aids and in the detergent field, but their main use is to be found in the detergent field.
• the term "granulate” is to be understood in its widest sense comprising the entire scope from small particles with a size of the order of magnitude around 10 ⁇ m to tablets with a size of the order of magnitude around 1 cm.
• Enzyme containing granulates are widely used in industry, mainly as dust free additives to detergents.
• One of the big problems in regard to enzyme containing granulates is the storage stability of the enzymes when the enzyme containing granulate is mixed with the other detergent components. Even if several methods for stabilization of the enzymatic activity have been devised, the stability of the enzymatic activity in the enzyme granulate containing detergents is still open to improvement.
• Another problem in regard to enzyme containing granulates is the color, as most enzyme containing granulates will be discolored, if not coated with e.g. Ti0 2 .
• a third problem in regard to enzyme containing granulates is the smell thereof. Even after a fairly good purification of the enzyme containing fermentation broth the finished product often exhibits an unagreeable strong smell.
• Anhydrous or substantially anhydrous slurries are widely used in industry, mainly as additives to liquid detergents.
• Aqueous slurries can be used as additives to liquid detergents, in the starch industry and in the food industry. If the slurry is aqueous the water activity or the ionic strenght in the slurry has to be controlled in such manner that the entire amount or substantially the entire amount of the crystalline enzyme is maintained in the crystalline form.
• a big problem in relation to liquid detergents is the stability of enzymes added to these.
• Several stabilization systems have been used in an attempt to overcome this problem. Within the field of low pH formulations both calcium, formate and borate stabilization has been used and are used. Within the higher pH range some of the inhibition methods are also used. But especially within structured liquids a hydrophobic encapsulation has been used, vide GB 2.186.884A. However, all these stabilization systems are open to improvement.
• Another big problem in regard to liquid, enzyme containing preparations is the color. Most liquid, enzyme containing preparations are colored due to impurities, usually with a dull, brownish color, and also, the color varies somewhat from batch to batch.
• the purpose of the invention is the provision of an enzyme containing preparation, which exhibits an improved stability, and which is colorless or almost colorless and of a high purity, and thus without any smell problems, and a detergent containing such enzyme containing preparation.
• the enzyme containing preparation according to the invention which contains at least one enzyme is characterized by the fact that at least 50% of the enzymatic activity of at least one enzyme is present in the preparation as enzyme crystals.
• the enzyme containing preparation according to the invention when present in a detergent, possesses an equally good or better enzyme stability than otherwise similar but less pure enzyme containing preparations. It is normally assumed that some of the impurities from the fermentation broth stabilize the enzyme, and that consequently it would be a disadvantage in regard to enzyme stability to purify the enzyme too much, and this assumption is correct. However, if a pure enzyme can be maintained as crystals in the preparations according to the invention it has been found that the stability is almost equal to or better than the stability of less pure preparations. Also, it has been found that the enzyme containing preparation according to the invention possesses improved color and smell characteristics, when the crystallization of the enzyme is performed without later introduction of impurities.
• the enzyme containing preparations according to the invention can be produced in any conventional manner, if only the conventional enzyme starting material, i.e. enzyme in the form of an amorphous powder, usually with a relatively large amount of impurities, or in the form of an enzyme solution or slurry, is substituted by an enzymatic starting material, in which at least 50% of the enzymatic activity is present as enzyme crystals.
• the preparation is a granulate, a non limiting list of such usable granulation methods is the previously cited US 4,106,991, US 4,661,452, DOS 2,060,095, and GB 1,362,365.
• a further advantage in relation to the preparation according to the invention is to be found in the washing process in a washing float with chlorine in the tap water.
• the chlorine will be consumed in the beginning of the washing cycle, and due to the fact that crystalline enzymes are dissolved slower in the washing float than enzymes usually used, the enzymes in the preparation according to the invention will not be present in dissolved form, before part of the chlorine has been consumed, and thus they will be protected from inactivation by the chlorine. Documentation for this will be presented later in this specification.
• the preparation contains a stabilizing agent for the enzyme(s).
• a stabilizing agent for the enzyme(s) for the enzyme(s).
• PVP polyvinyl pyrrolidone
• sucrose and Ca ++ can be used as stabilizing agents.
• the preparation contains a protease and at least one other enzyme, whereby substantially 100% of the proteolytic activity is present as crystals.
• the crystalline protease or nothing thereof will be dissolved in the preparation according to the invention, and thus, the stability of the other enzyme or the other enzymes in the preparation according to the invention will be improved in this embodiment. If the protease is Savinase ® and the preparation contains the lipase Lipolase ® as the other enzyme, and if the preparation is a slurry it has been found that in this embodiment of the preparation (with crystalline Savinase ® ) the lipase exhibits an excellent stability.
• the preparation according to the invention containing a protease and at least one protease sensitive enzyme substantially 100% of the protease sensitive enzyme or the protease sensitive enzymes are present as crystals. Only a small amount of the protease sensitive enzyme (s) or nothing thereof will be dissolved in the preparation according to the invention, and thus, the stability of the protease sensitive enzyme(s) in the preparation according to the invention will be improved in this embodiment. If the protease is Savinase ® and the preparation contains the lipase Lipolase ® as the other enzyme, and if the preparation is a granulate it has been found that in this embodiment of the preparation (with crystalline lipase) the lipase exhibits an excellent stability.
• more than 90% of the crystals possess a maximum crystal dimension between 0.1 ⁇ m and 500 ⁇ m, preferably between 1 ⁇ m and 100 ⁇ m.
• Such crystals are preferably prepared according to co-pending patent applications Nos. 847/90 and 848/90 (our refs. 3411.010-DK and 3411.020-DK), filed on the same date as this application, but they can also be prepared by means of other crystallization methods.
• the enzyme is a protease, lipase, amylase, cellulase, hemicellulase, pectinase, amidase or oxidase, or protein engineered variants of these. These enzymes are common enzymes used as additives in detergents.
• the enzyme is a protease, and the protease is a Subtilisin type protease.
• Examples are Savinase ® , Esperase ® , Alcalase ® , Subtilisin NOVO or protein engineered variants of these. These enzymes are preferred proteases in detergents.
• the enzyme is a lipase and the lipase is Lipolase ® .
• the preparation according to the invention at least 75%, preferably at least 90% of the enzymatic activity of at least one enzyme is present in the granulate as enzyme crystals, preferably of all enzymes.
• the stability of such preparations is excellent.
• the preparation according to the invention is a granulate. This preparation is well suited as an additive to a detergent in granulate form.
• the preparation is a slurry.
• the slurry is anhydrous or substantially anhydrous.
• the slurry is aqueous.
• the preparation is used as a detergent additive. This is the main use of the preparation according to the invention. Also the invention comprises a detergent, which contains the preparation according to the invention.
• the detergent is solid and contains the granulate according to the invention in a concentration of between 0.001 and 10 mg of enzyme protein/g of detergent, preferably between 0.005 and 5 mg of enzyme protein/g of detergent, most preferably from 0.01 to 1 mg of enzyme protein/g of detergent.
• these concentrations will usually be obtained by addition of between 0.01 and 10% w/w of the granulate to the detergent.
• the detergent is liquid and contains the anhydrous or substantially anhydrous slurry according to the invention in an amount of between 0.001 to 10 mg of enzyme protein per g of detergent, preferably from 0.005 to 5 mg of enzyme protein per g of detergent, most preferably from 0.01 to 1 mg of enzyme protein per g of detergent.
• Such liquid detergents exhibit a satisfactory stability of the enzyme.
• binders in relation to the granulate preparations according to the invention is a necessity, and optionally such binders can be carbohydrate binders, e.g. dextrins or cellulose derivatives, for instance hydroxypropyl cellulose, methyl cellulose or CMC.
• carbohydrate binders e.g. dextrins or cellulose derivatives, for instance hydroxypropyl cellulose, methyl cellulose or CMC.
• the KNPU proteolytic activity unit is defined in AF 101.10, which on request can be obtained from Novo Nordisk A/S, Denmark.
• the granulate is dried in a fluid bed to a water content below 1%, whereafter a light colored granulate is obtained with particle distribution: 11% > 1180 ⁇ m 17% > 1000 ⁇ m 25% > 850 ⁇ m 40% > 710 ⁇ m
• the granulate is finally sifted to get a product with the particle range 300 ⁇ m to 1000 ⁇ m and coated with 7% of PEG 4000 and 12% of a 1 :1 mixture of Ti0 2 and kaolin in a manner as described in US patent No. 4,106,991 , Example 22.
• the mixed dry components are sprayed with 3.6 kg of water.
• the moist mixture is exposed to a compacting and granulation influence from the multiple set of knives, as descibed in Example 1 of US patent no. 4,106,991.
• the granulate is dried in a fluid bed, and the part thereof defined as product fraction (in this cae 300- 900 ⁇ m) is separated for quality testing.
• product fraction in this cae 300- 900 ⁇ m
• the mixed dry components are sprayed with 3.0 kg of water.
• Lipolase ® is brighter than the color of the preparation in Example 3 (amorphous Lipolase ® ).
• the product fraction is coated for storage stability testing.
• the storage stability of the coated granulates produced according to Examples 2 and 3 is tested using accelerated conditions:
• Example 2 crystalline Lipolase ®
• Example 3 amorphous Lipolase ® EXAMPLE 4
• the mixed dry components are sprayed with 3.3 kg of water.
• the product fraction is coated for storage stability testing.
• the mixed dry components are sprayed with 0.7 kg of crystalline Savinase ® filter cake produced according to DK patent application no. 847/90 suspended in 2.9 kg of water.
• the product fraction is coated for storage stability testing.
• the mixed dry components are sprayed with 0.7 kg of crystalline Savinase ® filter cake produced according to DK patent application no. 847/90 suspended in 3.0 kg of water.
• the product fraction is coated for storage stability testing.
• Example 4 amorphous Savinase ® /- crystalline Lipolase ® 99 84 77
• Example 5 amorphous Savinase ® /- amorphous Lipolase ® 89 61 39
• Example 6 crystalline Savinase ® /- amorphous Lipolase ® 81 54 45
• Example 7 crystalline Savinase*/- crystalline Lipolase ® 95 84 77
• the granulates produced according to Examples 4 through 7, determined in regard to the protease sensitive enzyme Lipolase ® is tested under other accelerated conditions:
• Example 4 amorphous Savinase ® /- crystalline Lipolase ® 87 66 41
• Example 5 amorphous Savinase ® /- amorphous Lipolase* 51 15
• Example 6 crystalline Savinase ® /- amorphous Lipolase ® 46 15
• Example 7 crystalline Savinase*/- crystalline Lipolase ® 81 58 36
• Example 8 crystalline Savinase ®
• Example 9 amorphous Savinase ®
• the mixed dry components are sprayed with 0.354 kg of crystalline Durazym ® filter cake produced according to DK patent application no. 847/90, suspended in 1.5 kg of water, 0.07 kg of PVP K30 and 0.4 kg of carbohydrate binder.
• Example 10 crystalline Durazym ®
• Example 11 amorphous Durazym ®
• the mixed dry components are sprayed with 1.5 kg of crystalline Savinase ® filter cake produced according to DK patent application no. 847/90, suspended in 2.5 kg of water with 0.1 kg of Na 2 S0 and 0.2 kg of PVP K30.
• the mixed dry components are sprayed with 1.8 kg of carbohydrate binder, 0.2 kg of PVP K30 in 3.6 kg of water.
• Example 12 dry crystalline Savinase ® 60 58 52
• Example 13 crystalline Savinase ® 68 57 49
• Example 14 amorphous Savinase ® 60 51 42
• Example 12 dry crystalline Savinase*
• Example 13 crystalline Savinase ®
• Example 14 amorphous Savinase ®
• the liquid preparation Lipolase ® 100L in an amount of 1%, crystalline Savinase in an amount of 0.2% and dissolved Savinase ® in an amount of 0.625% was added to NOVO standard liquid detergent with builder with the following composition:
• the below indicated table shows the residual activity of the dissolved Lipolase ® in the liquid detergent after 3 days at 4 ⁇ C and 35 ⁇ C.
• This example illustrates the storage stability of aqueous and anhydrous Savinase ® slurries.
• the aqueous slurry base was 54% (NH 4 ) 2 S0 4 in deionized water.
• the anhydrous slurry base was 305 g of Surfactant T9, 140 g
• KNPU/g (%) KNPU/g (%) KNPU/g (%) KNPU/g (%) KNPU/g (%

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• 1990
  • 1990-12-21 WO PCT/DK1990/000340 patent/WO1991009941A1/en active IP Right Grant
  • 1990-12-21 EP EP91901708A patent/EP0506791B1/de not_active Expired - Lifetime
  • 1990-12-21 DE DE91901708T patent/DE69003253T2/de not_active Expired - Fee Related
  • 1990-12-21 DK DK91901708.7T patent/DK0506791T3/da active
  • 1990-12-21 ES ES91901708T patent/ES2044718T3/es not_active Expired - Lifetime
  • 1990-12-21 AT AT91901708T patent/ATE94206T1/de not_active IP Right Cessation
  • 1990-12-21 JP JP3502037A patent/JPH05502584A/ja active Pending

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