EP0478684B1 - Detergent additive granulate and detergent - Google Patents
Detergent additive granulate and detergent Download PDFInfo
- Publication number
- EP0478684B1 EP0478684B1 EP90910607A EP90910607A EP0478684B1 EP 0478684 B1 EP0478684 B1 EP 0478684B1 EP 90910607 A EP90910607 A EP 90910607A EP 90910607 A EP90910607 A EP 90910607A EP 0478684 B1 EP0478684 B1 EP 0478684B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granulate
- detergent
- enzyme
- detergent additive
- photobleaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 56
- 239000003599 detergent Substances 0.000 title claims abstract description 41
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 230000000996 additive effect Effects 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 108090000790 Enzymes Proteins 0.000 claims abstract description 24
- 102000004190 Enzymes Human genes 0.000 claims abstract description 24
- 229940088598 enzyme Drugs 0.000 claims description 23
- 108010059892 Cellulase Proteins 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 108091005804 Peptidases Proteins 0.000 claims description 3
- 229940106157 cellulase Drugs 0.000 claims description 3
- 108700023418 Amidases Proteins 0.000 claims description 2
- 239000004382 Amylase Substances 0.000 claims description 2
- 102000013142 Amylases Human genes 0.000 claims description 2
- 108010065511 Amylases Proteins 0.000 claims description 2
- 102000004882 Lipase Human genes 0.000 claims description 2
- 108090001060 Lipase Proteins 0.000 claims description 2
- 239000004367 Lipase Substances 0.000 claims description 2
- 102000004316 Oxidoreductases Human genes 0.000 claims description 2
- 108090000854 Oxidoreductases Proteins 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 2
- 102000005922 amidase Human genes 0.000 claims description 2
- 235000019418 amylase Nutrition 0.000 claims description 2
- 235000019421 lipase Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 10
- 238000004900 laundering Methods 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000005469 granulation Methods 0.000 description 10
- 239000000440 bentonite Substances 0.000 description 8
- 229910000278 bentonite Inorganic materials 0.000 description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001720 carbohydrates Chemical class 0.000 description 7
- 239000007844 bleaching agent Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003625 amylolytic effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000001461 cytolytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 230000002366 lipolytic effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000002797 proteolythic effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- HUVXQFBFIFIDDU-UHFFFAOYSA-N aluminum phthalocyanine Chemical compound [Al+3].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HUVXQFBFIFIDDU-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 builders Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating compounds
Definitions
- the concept of incorporation of a photobleaching agent in a detergent is known, reference being made to e.g. DE-A-3430773, EP-A-119746, and EP-A-87833.
- the photobleaching agent is inactive if not exposed to UV light, and thus, under normal conditions, the photobleaching agent will first be activated and function as a bleaching agent when the clean laundry is dried in the open. This is a clear advantage over the detergents with a normal bleach, which will function as a bleaching agent already in the washing solution and thus damage sensitive detergent additives, especially enzymes.
- photobleaching agents in detergents in solid form are not without problems, though.
- particles of pure photobleaching agent or particles of detergent additives, which contains photobleaching agents at the surface thereof will tend to adhere to the laundry due to a selective adhesion ability of the photobleaching agent to the laundry, and also such photobleaching agent will tend to stay with the laundry without being dissolved during the washing process.
- Most photobleaching agents possess a very intense color, and such photobleaching agents will create a most undesirable staining of the laundry.
- the photobleaching agent is colorless, the above indicated attachment thereof to the laundry during the washing process will create an uneven concentration of photobleaching agent on the laundry, and in that case an uneven overbleaching action will take place when the laundry is dried in the open.
- the detergent additive granulate according to the invention is a co-granulate containing at least one enzyme and at least one photobleaching agent, the co-granulate being coated.
- the photobleaching agent can be any photobleaching agent, e.g. Tinolux BBS, vide the following examples, zinc phthalocyanine sulfonate (ZPS), and aluminum phthalocyanine sulfonate (APS).
- Tinolux BBS zinc phthalocyanine sulfonate
- ZPS zinc phthalocyanine sulfonate
- APS aluminum phthalocyanine sulfonate
- Tinolux and the later indicated materials Arbocel, Speswhite, and Glascol are trade marks.
- the detergent additive granulate according to the invention will fulfil the above objective in an especially advantageous manner, if produced by means of a drum granulator, as will later be described in more detail.
- the detergent additive granulate can and will usually contain other components besides the components listed above, provided that these components do not damage the enzyme and/or the photobleaching agent.
- aqueous fabric washing detergent which can contain both enzymes and a photobleaching agent.
- this detergent is aqueous, and the above problem, which is solved according to the invention, does not appear at all in relation to aqueous detergents, which exhibit other problems, e.g. stability problems.
- EP-A-119.746 describes a detergent powder which contains both photobleach and enzyme.
- the first step during the production of this washing powder is the formation of the aqueous crutcher slurry, consisting of surfactants, builders, fillers, and a solution of the photobleach.
- This crutcher slurry is spray-dried, whereby the so-called base powder is formed.
- the enzyme which may optionally be added vide page 4, line 29 in EP-A-119.746) has to be added as enzyme containing particles separate from the base powder, due to the fact that the enzyme activity in the base powder would be reduced severely or lost completely, if the enzyme was added to the crutcher solution.
- the EP-A-119.746 contains enzyme free, photobleaching agent containing particles and photobleaching agent free enzyme containing particles. It has been found that the problem of staining and overbleaching is not completely solved in relation to this prior art washing powder.
- DE-A-28 13 198 describes a bleaching agent which contains a special photoactivator.
- This bleaching agent is produced by co-granulation of all constituents of the bleaching agent to a co-granulate or by granulation of a single constituent on a basis detergent component, whereas according to the invention two sensitive constituents of the detergent are selected, i.e. the enzyme and the photobleaching agent, and co-granulated.
- the detergent additive granulate according to the invention can be produced by co-granulation in many ways, e.g. as indicated in the following.
- the photobleaching agent is added as an aqueous solution, preferably as part of the granulation water.
- the usual coating agents may be used, e.g. the coating agents described in DK-A-0121/88, DK-A-1377/88, and DK-A-378/88.
- the enzyme is one or more of the enzymes protease, amylase, lipase, cellulase, oxidase, and amidase. These are the most common enzymes used in the detergent additive.
- detergent additive granulate according to the invention between 2 and 40% w/w of cellulose fibres are incorporated into the granulate.
- a granulate of this kind can be produced according to US-A-4,106,991 (Novo Nordisk A/S, Denmark). In this manner a dust free granulate is obtained which can easily be produced in an industrial scale.
- the invention comprises a detergent which contains the detergent additive granulate according to the invention.
- the concentration of the detergent additive is between 0.05 and 5% w/w. In this manner the object of the invention is fulfilled, and also, the photobleaching effect is fully satisfactory.
- Example 1 In the following the production of the detergent additive granulate according to the invention is illustrated in Examples 1, 4, 5, 7, 9, and 10, and the use of the detergent additive granulate is illustrated in Example 11.
- a powder mixture containing a proteolytic enzyme and with the following composition 8.0 kg of SAVINASE® with an activity of 36.1 KNPU/g 6.0 kg of fibrous cellulose Arbocel BC 200 1.6 kg of kaolin, Speswhite ECCI 2.4 kg of carbohydrate binder 20.6 kg of finely ground sodium sulphate is transferred to a 130 liter Lodige mixer FM 130 and granulated with 9.7 kg of a granulation liquid made up by mixing of 2.0 kg of Tinolux BBS (liquid), Ciba-Geigy 0.9 kg of carbohydrate binder 7.0 kg of water all other conditions during the granulation being identical to Example 1 in US-A-4.106.991 (Novo Nordisk A/S, Denmark).
- KNPU is an activity unit for proteolytic activity, described in the document AF 220/1-GB
- KLU is an activity unit for lipolytic activity, described in the document AF 95/5
- CSU is an activity unit for cellulolytic activity, described in the document AF 187/3
- KNU is an activity unit for amylolytic activity, described in the document AF 207/1, whereby all the cited documents are available on request from Novo Nordisk, Novo Allé, DK-2880 Bagsvaerd, Denmark.
- Tinolux BBS is a photobleaching agent, which is a derivative of tetrabenzo-tetraazaporphine.
- the moist granulate is dried on a fluid bed to a water content below 1%, and the sieve fraction of the granulate between 300 ⁇ m and 900 ⁇ m is taken out as a product.
- This product is coated with 6.2% of polyethylene glycol (PEG 4000) and 10% of kaolin (Speswhite, ECC) by means of the method described in Example 22 in US-A-4.106.991 (Novo Nordisk A/S, Denmark).
- the granulate is further provided with a film coating consisting of 170 ppm of duasynic acid green and 0.25% of hydroxypropyl cellulose.
- the final preparation exhibited a proteolytic activity of 5.7 KNPU/g.
- a powder mixture containing a lipolytic enzyme and with the following composition 0.75 kg of LIPOLASE® with an activity of 860 KLU/g 2.25 kg of fibrous cellulose Arbocel BC 200 1.50 kg of bentonite ECCI ASB350 0.90 kg of carbohydrate binder 8,90 kg of finely ground sodium sulphate is transferred to a 50 liter Lödige mixer FM 50 and granulated with 3.4 kg of a granulation liquid made up by mixing of 0.7 kg of Tinolux BBS 0.7 kg of carbohydrate binder 2.0 kg of water
- the granulation is carried out as described in Example 1, except for the size of the mixer.
- the granulate is dried and sifted as described in Example 1, whereby a granulate with an activity of 31.2 KLU/g is obtained.
- a powder mixture containing a cellulolytic enzyme and with the following composition 3.00 kg of cellulase with an activity of 5340 CSU/g 2.25 kg of fibrous cellulose Arbocel BC 200 0.60 kg of kaolin ECCI Speswhite 0.60 kg of carbohydrate binder 8,85 kg of finely ground sodium sulphate is transferred to a 50 liter Lödige mixer FM 50 and granulated with 3.4 kg of a granulation liquid made up by mixing of 0.83 kg of Tinolux BBS 0.30 kg of carbohydrate binder 3.00 kg of water
- the granulation is carried out as described in Example 1, except for the size of the mixer.
- the granulate is dried and sifted as described in Example 1.
- Example 2 1 kg of dry sifted (300-1000 ⁇ m) granulate produced as described in Example 2 is coated in a 5 liter Lödige mixer according to the method described in US-A-4,106,991 (Novo Nordisk A/S, Denmark), example 22.
- Example 4 1 kg of dry sifted (300-1000 ⁇ m) granulate produced as described in Example 3 is coated as described in Example 4.
- Example 6 5 kg of a Tinolux/bentonite coated granulate produced as described in Example 6 is further coated with 100 g of bentonite and 45 g of Glascol LS22P (dry matter) by spraying with an emulsion/suspension consisting of 100 g of bentonite ASB 350 100 g of Glascol LS22P (45% microemulsion) 500 g of water by means of the same fluidized bed coating technique as described in Example 6.
- Example 8 5 kg of a Tinolux coated granulate produced as described in Example 8 is further coated with 200 g of bentonite and 135 g of Glascol LS22P (dry matter) by spraying with an emulsion/suspension consisting of 200 g of bentonite ASB 350 300 g of Glascol LS22P (45% microemulsion) 1000 g of water by means of the same fluidized bed coating technique as described in Example 6.
- a powder composition containing an amylolytic enzyme and with the following composition is prepared for extrusion according to Example 4 in US-A-4,661,452 (Novo Nordisk A/S, Denmark).
- 0.500 kg of BAN with an activity of 4900 KNU/g 0.100 kg of titanium dioxide 0.275 kg of a carbohydrate binder 0.500 kg of calcium carbonate, Sturcal L 0.350 kg of anhydrous calcium sulphate 0.125 kg of sodium carboxymethyl cellulose, Hercules 7H 2.725 kg of finely ground sodium sulphate by spraying with 600 g Tinolux BBS containing 100 g of PVP K30 and finally spraying the moist mixture with 200 g of coconut monoethanol amide.
- the hot (55°C) moist mixture is extruded using a pellet press type extruder (Simon-Heesen type Monoroll Labor).
- a pellet press type extruder Simon-Heesen type Monoroll Labor.
- the original Simon-Heesen pellet die with 8 mm holes is equipped with a screen plate with 0.8 mm holes on the inside, which screen is supported by the die.
- the extrudate After extrusion the extrudate is allowed to cool by blowing cold air through it. After cooling to room temperature it is transferred to the Marumerizer®, which breaks the extrudate to a short sized noodle like product, which is compact and exhibits a well rounded surface. Finally the product is dried in a fludized bed drier.
- the product is coated with a protective coating as described in example 22 of US-A-4,106,991 (Novo Nordisk A/S, Denmark) or in WO-A-89/08694 (Novo Nordisk A/S, Denmark) or in WO-A-89/08695 (Novo Nordisk A/S, Denmark).
- This example is a spotting example illustrating the use of the detergent additive granulate according to the invention.
- Granules from Example 1 are added to a solution of a standard powder detergent in a jar. A piece of white cotton textile is placed on the bottom of the jar. The spotting from the granules on the white textile is evaluated after 1 minute according to the grades shown in the legend.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Enzymes And Modification Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK3062/89 | 1989-06-21 | ||
DK306289A DK306289D0 (da) | 1989-06-21 | 1989-06-21 | Detergentadditiv i granulatform |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0478684A1 EP0478684A1 (en) | 1992-04-08 |
EP0478684B1 true EP0478684B1 (en) | 1993-12-08 |
Family
ID=8118654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90910607A Expired - Lifetime EP0478684B1 (en) | 1989-06-21 | 1990-06-14 | Detergent additive granulate and detergent |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0478684B1 (tr) |
JP (1) | JPH04506229A (tr) |
KR (1) | KR920701410A (tr) |
AT (1) | ATE98295T1 (tr) |
AU (1) | AU641672B2 (tr) |
BR (1) | BR9007470A (tr) |
DE (1) | DE69005112T2 (tr) |
DK (2) | DK306289D0 (tr) |
EG (1) | EG19045A (tr) |
ES (1) | ES2046788T3 (tr) |
MX (1) | MX21242A (tr) |
MY (1) | MY105995A (tr) |
NZ (1) | NZ234159A (tr) |
PT (1) | PT94439B (tr) |
TR (1) | TR27368A (tr) |
WO (1) | WO1990015856A1 (tr) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5167854A (en) * | 1985-08-21 | 1992-12-01 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
US5376288A (en) * | 1989-06-21 | 1994-12-27 | Noro Nordisk A/S | Detergent additive granulate and detergent |
GB9220669D0 (en) * | 1992-09-30 | 1992-11-11 | Unilever Plc | Detergent composition |
DK5593D0 (da) * | 1993-01-18 | 1993-01-18 | Novo Nordisk As | Granulat |
CN1149314A (zh) * | 1994-05-31 | 1997-05-07 | 诺沃挪第克公司 | 染料转移抑制制剂以及含这样的制剂的洗涤剂组合物 |
WO2000022104A1 (fr) * | 1998-10-09 | 2000-04-20 | Kao Corporation | Particules d'enzyme |
DE19855677A1 (de) * | 1998-12-02 | 2000-06-08 | Henkel Kgaa | Herstellung Aufheller-haltiger Waschmittel-Granulate |
CN1384871A (zh) * | 1999-06-21 | 2002-12-11 | 宝洁公司 | 涂敷的洗涤剂颗粒的制备方法 |
US6767882B1 (en) | 1999-06-21 | 2004-07-27 | The Procter & Gamble Company | Process for producing coated detergent particles |
IT1319655B1 (it) | 2000-11-15 | 2003-10-23 | Eurand Int | Microsfere di enzimi pancreatici con elevata stabilita' e relativometodo di preparazione. |
GB2374082A (en) * | 2001-04-04 | 2002-10-09 | Procter & Gamble | Particles for a detergent product |
GB0314210D0 (en) | 2003-06-18 | 2003-07-23 | Unilever Plc | Laundry treatment compositions |
SG186648A1 (en) | 2007-02-20 | 2013-01-30 | Aptalis Pharma Ltd | Stable digestive enzyme compositions |
US10087493B2 (en) | 2008-03-07 | 2018-10-02 | Aptalis Pharma Canada Ulc | Method for detecting infectious parvovirus in pharmaceutical preparations |
UA111726C2 (uk) | 2010-10-01 | 2016-06-10 | Апталіс Фарма Лімітед | Препарат панкреліпази низької сили з кишковорозчинним покриттям |
AU2012293325B2 (en) | 2011-08-08 | 2015-05-07 | Allergan Pharmaceuticals International Limited | Method for dissolution testing of solid compositions containing digestive enzymes |
US10993996B2 (en) | 2013-08-09 | 2021-05-04 | Allergan Pharmaceuticals International Limited | Digestive enzyme composition suitable for enteral administration |
WO2015193730A1 (en) | 2014-06-19 | 2015-12-23 | Aptalis Pharma Ltd. | Methods for removing viral contaminants from pancreatic extracts |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1075405A (en) * | 1977-03-28 | 1980-04-15 | John F. Goodman | Photoactivated bleach-compositions and process |
GR78065B (tr) * | 1982-02-19 | 1984-09-26 | Unilever Nv | |
GB8304631D0 (en) * | 1983-02-18 | 1983-03-23 | Unilever Plc | Detergent powder |
-
1989
- 1989-06-21 DK DK306289A patent/DK306289D0/da not_active Application Discontinuation
-
1990
- 1990-06-14 AU AU59601/90A patent/AU641672B2/en not_active Ceased
- 1990-06-14 AT AT90910607T patent/ATE98295T1/de active
- 1990-06-14 ES ES199090910607T patent/ES2046788T3/es not_active Expired - Lifetime
- 1990-06-14 WO PCT/DK1990/000149 patent/WO1990015856A1/en active IP Right Grant
- 1990-06-14 EP EP90910607A patent/EP0478684B1/en not_active Expired - Lifetime
- 1990-06-14 DK DK90910607.2T patent/DK0478684T3/da active
- 1990-06-14 BR BR909007470A patent/BR9007470A/pt not_active Application Discontinuation
- 1990-06-14 KR KR1019910701466A patent/KR920701410A/ko not_active Application Discontinuation
- 1990-06-14 JP JP2509933A patent/JPH04506229A/ja active Pending
- 1990-06-14 DE DE90910607T patent/DE69005112T2/de not_active Expired - Fee Related
- 1990-06-20 MX MX2124290A patent/MX21242A/es unknown
- 1990-06-20 MY MYPI90001045A patent/MY105995A/en unknown
- 1990-06-20 EG EG36690A patent/EG19045A/xx active
- 1990-06-20 NZ NZ234159A patent/NZ234159A/en unknown
- 1990-06-20 PT PT94439A patent/PT94439B/pt not_active IP Right Cessation
- 1990-07-17 TR TR00591/90A patent/TR27368A/tr unknown
Also Published As
Publication number | Publication date |
---|---|
DK0478684T3 (da) | 1994-04-18 |
DK306289D0 (da) | 1989-06-21 |
EP0478684A1 (en) | 1992-04-08 |
NZ234159A (en) | 1992-01-29 |
PT94439A (pt) | 1991-02-08 |
KR920701410A (ko) | 1992-08-11 |
WO1990015856A1 (en) | 1990-12-27 |
ATE98295T1 (de) | 1993-12-15 |
JPH04506229A (ja) | 1992-10-29 |
EG19045A (en) | 1994-12-30 |
AU5960190A (en) | 1991-01-08 |
ES2046788T3 (es) | 1994-02-01 |
MX21242A (es) | 1993-11-01 |
AU641672B2 (en) | 1993-09-30 |
BR9007470A (pt) | 1992-06-16 |
PT94439B (pt) | 1997-02-28 |
MY105995A (en) | 1995-02-28 |
TR27368A (tr) | 1995-01-17 |
DE69005112D1 (de) | 1994-01-20 |
DE69005112T2 (de) | 1994-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0478684B1 (en) | Detergent additive granulate and detergent | |
US5376288A (en) | Detergent additive granulate and detergent | |
EP0404806B1 (en) | Stabilized particulate composition | |
EP0270608B1 (en) | Coated detergent enzymes | |
JP2647695B2 (ja) | 酵素含有粒質物 | |
US4707287A (en) | Dry bleach stable enzyme composition | |
JP2801395B2 (ja) | 洗剤添加剤粒質物およびその製法 | |
US5324649A (en) | Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof | |
US5318714A (en) | Stabilized particulate composition | |
EP2007863B1 (de) | Granulat eines sensitiven wasch- oder reinigungsmittelinhaltsstoffs | |
EP0506791B1 (en) | Enzyme containing preparation and detergent containing such preparation | |
EP0206418B1 (en) | Dry bleach and stable enzyme granular composition | |
US4767557A (en) | Dry bleach and stable enzyme granular composition | |
JPH07506124A (ja) | 粒状組成物 | |
US6656898B1 (en) | Enzyme composite particles having an acidic barrier and a physical barrier coating | |
JPH10502114A (ja) | 複数の酵素を含有する顆粒の製法 | |
JP2003504050A (ja) | 酵素含有顆粒の調製方法 | |
CN1742084B (zh) | 颗粒的稳定化 | |
US4911851A (en) | Detergent compatible, dryer released fabric softening/antistatic agents | |
US3781228A (en) | Laundry product containing enzyme | |
EP0680510A1 (en) | Enzyme containing granulate, method for production thereof, and use thereof | |
CN1152334A (zh) | 多酶颗粒及其制法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19910930 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19930312 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE |
|
REF | Corresponds to: |
Ref document number: 98295 Country of ref document: AT Date of ref document: 19931215 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 69005112 Country of ref document: DE Date of ref document: 19940120 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2046788 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed | ||
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19940630 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
EAL | Se: european patent in force in sweden |
Ref document number: 90910607.2 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19960523 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19960605 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19960617 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19960619 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19960624 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19960625 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 19960627 Year of fee payment: 7 Ref country code: AT Payment date: 19960627 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19960630 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19960702 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970614 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970614 Ref country code: AT Effective date: 19970614 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19970615 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 19970616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970630 Ref country code: BE Effective date: 19970630 |
|
BERE | Be: lapsed |
Owner name: NOVO NORDISK A/S Effective date: 19970630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19980101 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19970614 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980227 |
|
EUG | Se: european patent has lapsed |
Ref document number: 90910607.2 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19980101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980303 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20000201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050614 |