WO1994016064A1 - Enzyme containing granulate, method for production thereof, and use thereof - Google Patents
Enzyme containing granulate, method for production thereof, and use thereof Download PDFInfo
- Publication number
- WO1994016064A1 WO1994016064A1 PCT/DK1994/000030 DK9400030W WO9416064A1 WO 1994016064 A1 WO1994016064 A1 WO 1994016064A1 DK 9400030 W DK9400030 W DK 9400030W WO 9416064 A1 WO9416064 A1 WO 9416064A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- granulate
- cellulase
- protease
- fact
- protein
- Prior art date
Links
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
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
Definitions
- the invention comprises an enzyme containing granulate, a method for production thereof, and a use thereof. It has been found that a cellulase containing granulate exhibits an unsatisfactory low enzymatic stability under humid conditions if present in a detergent.
- an enzyme containing granulate in which the enzyme comprises a cellulase, and in relation to which the cellulase stability under humid conditions in admixture with a detergent is improved.
- the enzyme containing granulate according to the invention is characterized by the fact that it is a co-granulate comprising an intimate mixture of at least one cellulase and at least one protease, and that it does not contain a photobleaching agent.
- the cellulases and the proteases used as components in the enzyme containing granulate according to the invention can be produced conventionally, i.e. by means of naturally occurring microorganisms, or by means of protein engineering.
- the granulate according to the invention exhibits a better cellulase stability under humid conditions in admixture with a detergent than the prior art granulates.
- protease might digest the cellulase in the co-granulate and thus impair the cellulase stability, this is a surprising result.
- the stabilization improving effect related to the granulate according to the invention is not found in a mixture of a cellulase granulate and a protease granulate. Thus, it is imperative for the invention that the
- 10 granulate is a co-granulate with the composition indicated.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the granulate is coated.
- the granulate can be coated by means of any of the usually used coating agents, e.g. the coating agents described in Australian Patent No. 459399, page 3, lines 4-11. In this manner an
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the cellulase is one or more of the cellulases producible by means of Humicola insolens DSM 1800, DSM 2068 or DSM 2069 or natural or protein engineered variants thereof. It has been found that these cellulases
- the definition of the cellulase activity unit S-CEVU appears from AF 302.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the cellulase is neutral or alkaline.
- a neutral or alkaline cellulase is a cellulase, the pH optimum of which is between 6 and
- proteases are especially well suited as components of enzymatic detergent additives, due to their excellent effect in the washing liquid.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the protease is Savinase ® (producible by means of B. lentus), Alcalase ® (producible by means of B. licheniformis) or subtilisin Novo
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the protease is a natural or protein engineered variant of a trypsin type protease. These proteases exhibit a good stabilizing effect.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the protease is producible by means of Fusarium oxyspor ⁇ m. These proteases exhibit a good stabilizing effect and can be obtained as SP 387 from NOVO NORDISK A/S.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the weight proportion between the protease protein and the cellulase protein is at least 0.01, preferably at least 0.1. No satisfactory stabilizing effect has been seen with a weight proportion between the protease protein and the cellulase protein less than 0.01.
- a preferred embodiment of the granulate according to the invention is characterized by the fact that the granulate also contains PVP, preferably in an amount between 0.001 and 0.1 g/g of granulate. It has been found that the effect of
- PVP is a further improvement of the cellulase stability under humid conditions in admixture with a detergent.
- the invention comprises a method for production of the granulate according to the invention, which is characterized by the fact that an aqueous solution containing at least one of the enzymes cellulase and protease is sprayed onto a solid core in a granulating equipment.
- the core shall contain a protease, if the aqueous solution contains a cellulase only, and vice versa.
- the core may be enzyme free, if the aqueous solution contains both a cellulase and a protease.
- the invention comprises a use of the granulate according to the
- the granulate according to the invention can be used as a detergent additive in any detergent, e.g. both detergents with and without oxidizing agents.
- a preferred embodiment of the use according to the invention is characterized by the fact that the granulate is added in an amount of between 0.1 and 5% w/w, related to the total detergent weight. This corresponds to the concentrations of enzymatic additive in a commercial detergent.
- WO 90/15856 describes a co-granulate, which among many possibilities may contain both a cellulase and a protease. This prior art co-granulate, however, always contains a photobleaching agent and thus differs significantly from the invention.
- Danish Patent No. 157937 describes a granulate with a core and a shell, in which the core may contain a cellulase and the shell may contain a protease.
- this granulate is not a co-granulate, and it does not comprise the intimate mixture of the cellulase and the protease, which is found in the granulate according to the invention.
- the cellulase stability of this prior art granulate is inferior in comparison to the cellulase stability of the granulate according to the invention. Documentation for this will be presented later in this specification.
- WO 90/09440 describes a granulate with a core and a shell, in which the core contains one enzyme and the shell contains another enzyme.
- this granulate is not a co-granulate, it contains a sustained release coating between the core and the shell, and it does not comprise the intimate mixture of the two enzymes which is found in the granulate according to the invention. Accordingly, it has been found that the cellulase stability of this prior art granulate is inferior in comparison to the cellulase stability of the granulate according to the invention.
- the invention will be illustrated by the following examples. In order to demonstrate the stability improving effect provided by means of the invention directly, some of the examples are examples illustrating the invention, i.e. Examples 1, 2, 6, 7, 9, 12, 15, 16, 17, 19, and 20, and some of the examples are comparison examples illustrating the prior art, i.e. Examples 3, 4, 5, 8, 10, 11 , 13, 14, and 18.
- the cellulase activity S-CEVU is measured according to AF 302; the protease activity AU is measured according to AF 218, the protease activity KNPU is measured according to AF 220, the amylase activity KNU is measured according to AF 214, and the lipase activity KLU is measured according to AF 95.
- the humid granulate is dried at 60°C to a water content of less than 3%.
- the dry granulate is sieved to a particle size range between 300 and
- a part of the wanted product is coated in the following manner. 2 kg of the wanted product is heated to 75-80°C in a 5 litres heat jacketed L ⁇ dige mixer, and this temperature is maintained during the entire coating process.
- the heated granulate is mixed with 100 g of melted PEG 4000 followed by a powdering with 250 g of Ti0 2 and a subsequent addition of 20 g of PEG 4000.
- the granulate is finally cooled to room temperature in a fluid bed and siftet to a particle size range of 300-1000 ⁇ m.
- the obtained granulate exhibited a weight proportion between Alcalase ® protein and cellulase protein of approximately 4.4, a cellulase activity of 2690 S-CEVU/g, and a protease activity of 2.0 AU/g.
- Example 1 The above indicated components are granulated in a FM 50 L ⁇ dige mixer as in Example 1. Also, as in Example 1 lactose (only 50% of the amount used in Example 1, though) and PVP is dissolved in a mixture of liquid cellulase 10 concentrate and water.
- the thus formed granulate is dried in a fluid bed to a water content of below 3%, and subsequently sieved in order to obtain a product with a particle size range from 300 to 1000 ⁇ m.
- a part of the wanted product is coated in the following manner. 2 kg
- the heated granulate is mixed with 100 g of melted PEG 4000 followed by a powdering with 250 g of Ti0 2 and a subsequent addition of 20 g of PEG 4000.
- the granulate is finally cooled to room temperature in a fluid bed and 0 siftet to a particle size range of 300-1000 ⁇ m.
- the obtained granulate exhibited a weight proportion between Savinase ® protein and cellulase protein of approximately 2.1. 5
- a weight proportion between Savinase ® protein and cellulase protein of approximately 2.1. 5
- a blend of a cellulase granulate and a protease granulate in the presence of a detergent has been used.
- the experimental conditions were as follows.
- the granulate according to the invention to be tested (Examples 1 and 2) is weighed into a series of glasses with approx. 3200 S-CEVU/glass.
- 8.0 g of a detergent, which is a compact zeolite built detergent without bleach is then added to each glass, and the glasses are closed with a lid. Subsequently, the content of the closed glasses is mixed by shaking. The lids are removed, and then the glasses are introduced into a climate room at 80% relative humidity and 35°C. After storage for a certain number of days, the whole content of each glass is analyzed for cellulase activity.
- the prior art granulates to be tested are blends of granulates each of which contains only one enzyme component. Then granulates are produced as indicated in Example 2 with the exception that only one enzyme is added. Thus, in case a Savinase granulate is to be produced, the cellulase is omitted and replaced by approximately the same amount of water, and in case a cellulase granulate is to be produced, the Savinase is omitted and replaced by the same amount of sodium sulphate.
- Example 4 are not examples according to the invention because no protease is present in the list of components. Instead skim milk powder is used in order to investigate, if skim milk powder showed any stability improving effect on the cellulase.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between casein protein and cellulase protein of approximately 7.9 and a cellulase activity of 971 S- CEVU/g.
- a powder mixture with the following composition 1.70 kg fibrous cellulose, ARBOCEL BC 200 0.64 kg of CaC0 3 CALOFORT type L 8.60 kg finely ground sodium sulphate 3.80 kg skim milk powder
- Carezyme ® is a cellulase preparation produced according to WO 10 91/17243. The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between casein protein and cellulase protein of approximately 15 and a cellulase activity of 1600 S- CEVU/g.
- This example is not an example according to the invention because no protease is present in the list of components. Instead gelatine is used in order to investigate, if gelatine showed any stability improving effect on the cellulase.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between gelatine protein and cellulase protein of approximately 2.3 and a cellulase activity of 1096 S- CEVU/g.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between Alcalase ® protein and cellulase protein of approximately 2.3, a cellulase activity of 10 1790 S-CEVU/g and a protease activity of 0.867 AU/g.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between protease protein and cellulase protein of approximately 0.32, a cellulase activity of 3900 S- CEVU/g and a protease activity of 1.14 KNPU/g.
- Example 2 0.24 kg PVP ' KOLIDON K30 0.64 kg carbohydrate binder 1.30 kg Amylase BAN concentrate 2.00 kg aqueous Carezyme ® concentrate The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between amylase protein and cellulase protein of approximately 0.16, a cellulase activity of 4790 S- CEVU/g and an amylase activity of 48.8 KNU/g.
- Example 2 The granulation is carried out as described in Example 1.
- the granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between protease protein and cellulase protein of approximately 0.43, a cellulase activity of 4900 S- CEVU/g and a protease activity of 0.305 AU/g. k )
- the reference is identical to Example 8, but with Na 2 S0 4 instead of BAN
- a reference T-granulate is produced as described in Example 1 but without protease.
- This PEG 4000 coated granulate is further spray coated on the outside of the granules with Savinase ® in a fluid bed.
- the obtained granulate exhibits a weight proportion between protease protein and cellulase protein of approximately 0.7, a cellulase acitivty of 5100 S- CEVU/g, and a protease activity of 3.5 KNPU/g.
- the obtained granulate is a co-granulate comprising a cellulase and a protease, but the cellulase and protease are not intimately mixed, becauase the cellulase is in the core and the protease (Savinase ® ) is in the coating. For that reason the granulate is a reference granulate, as above indicated.
- the granulate is produced as in Example 10, except for the fact that twice the amount of Savinase ® is coated on the outside of the granules.
- the obtained granulate exhibited a weight proportion between protease protein and cellulase protein of approximately 1.4, a cellulase activity of 4800 S- CEVU/g, and a protease activity of 6.9 KNPU/g.
- a granulate was produced as described in Example 1 , except for the fact that the amounts of cellulase, water and protease are adjusted to generate the following activities: 618 S-CEVU/g (cellulase) and 3.19 AU/g (protease).
- the weight proportion between protease protein and cellulase protein was approximately 30.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between amylase protein and cellulase protein of approximately 0.60, a cellulase activity of 4700 S- CEVU/g and an amylase activity of 60 KNU/g.
- Lipolase ® a lipase
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- the obtained granulate exhibited a weight proportion between lipase protein and cellulase protein of approximately 0.51 , a cellulase activity of 5060 S- CEVU/g and a lipase activity of 35 KLU/g.
- the cellulase stability improving effect is a selective protease effect, because other enzymes than protease and other proteins do not generate the cellulase stability improving effect.
- the co-granulate according to the invention necessarily has to comprise an intimate mixture of cellulase and ' protease in order to generate the cellulase stability improving effect, vide Example 10.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- a granulate with an activity of 5900 S-CEVU/g and 1.80 KNPU/g was produced.
- the weight proportion between protease protein and cellulase protein was approximately 0.44.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- a granulate with an activity of 4300 S-CEVU/g and 0.14 AU/g was produced.
- the weight proportion between protease protein and cellulase protein was approximately 0.19.
- a granulate is produced as described in Example 15, but Durazyme ® protease is used instead of Esperase ® protease. At the same time is used 11.1 kg sodium sulfate and 0.68 kg kaolin.
- a granulate with an activity of 4200 S-CEVU/g and 2.6 DPU/g was produced.
- Example 2 The granulation is carried out as described in Example 1. The granulate is dried and sifted and finally coated as described in Example 2.
- This granulate is produced as described in Example 18 but to the powder mixture is added 0.40 kg Alcalase ® powder concentrate instead of 0.40 kg sodium sulfate. A granulate with an activity of 1910 S-CEVU/g and 0.22 AU/g was produced.
- a granulate with an activity of 2300 S-CEVU/g and 0.12 AU/g was produced.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94904998A EP0680510A1 (en) | 1993-01-18 | 1994-01-17 | Enzyme containing granulate, method for production thereof, and use thereof |
JP6515621A JPH08505526A (en) | 1993-01-18 | 1994-01-17 | Enzyme-containing granules, their production and their use |
FI953457A FI953457A0 (en) | 1993-01-18 | 1995-07-17 | Enzyme-containing granulate, its preparation method and its use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK55/93 | 1993-01-18 | ||
DK5593A DK5593D0 (en) | 1993-01-18 | 1993-01-18 | GRANULES |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994016064A1 true WO1994016064A1 (en) | 1994-07-21 |
Family
ID=8089224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DK1994/000030 WO1994016064A1 (en) | 1993-01-18 | 1994-01-17 | Enzyme containing granulate, method for production thereof, and use thereof |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0680510A1 (en) |
JP (1) | JPH08505526A (en) |
DK (1) | DK5593D0 (en) |
FI (1) | FI953457A0 (en) |
WO (1) | WO1994016064A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0622450A2 (en) * | 1993-04-29 | 1994-11-02 | Amway Corporation | Detergents and methods for producing the same |
WO1996000772A1 (en) * | 1994-06-28 | 1996-01-11 | Henkel Kommanditgesellschaft Auf Aktien | Multiple enzyme granulates and their production |
WO2013007594A1 (en) | 2011-07-12 | 2013-01-17 | Novozymes A/S | Storage-stable enzyme granules |
EP2674476A1 (en) * | 2012-06-11 | 2013-12-18 | The Procter & Gamble Company | Detergent composition |
US9752103B2 (en) | 2013-06-11 | 2017-09-05 | The Procter & Gamble Company | Detergent composition |
CN112980903A (en) * | 2021-03-11 | 2021-06-18 | 哈尔滨商业大学 | Microwave-assisted bio-enzyme catalytic reaction verification method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013087178A (en) * | 2011-10-17 | 2013-05-13 | Kankyo Koken:Kk | Detergent for beverage container and method for cleaning beverage spouting device |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990015856A1 (en) * | 1989-06-21 | 1990-12-27 | Novo Nordisk A/S | Detergent additive granulate and detergent |
WO1992018599A1 (en) * | 1991-04-22 | 1992-10-29 | Novo Nordisk A/S | A detergent additive containing a cellulase and a protease |
-
1993
- 1993-01-18 DK DK5593A patent/DK5593D0/en not_active Application Discontinuation
-
1994
- 1994-01-17 JP JP6515621A patent/JPH08505526A/en active Pending
- 1994-01-17 EP EP94904998A patent/EP0680510A1/en not_active Withdrawn
- 1994-01-17 WO PCT/DK1994/000030 patent/WO1994016064A1/en not_active Application Discontinuation
-
1995
- 1995-07-17 FI FI953457A patent/FI953457A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990015856A1 (en) * | 1989-06-21 | 1990-12-27 | Novo Nordisk A/S | Detergent additive granulate and detergent |
WO1992018599A1 (en) * | 1991-04-22 | 1992-10-29 | Novo Nordisk A/S | A detergent additive containing a cellulase and a protease |
Non-Patent Citations (1)
Title |
---|
Dialog Information Services, File 351, World Patent Index, Dialog Accession No. 004727048, (NAGS) NAGASE SEIKAGAKU), "Granular Enzyme Compsn. Mfr. by Placing Shaped Seed Grains in Fluidised Bed Spraying, Coating and Drying Appts. and Spraying Enzyme-Contg. Soln. over Grains"; & JP,A,61 162 185, 860722, 8635. * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0622450A2 (en) * | 1993-04-29 | 1994-11-02 | Amway Corporation | Detergents and methods for producing the same |
WO1996000772A1 (en) * | 1994-06-28 | 1996-01-11 | Henkel Kommanditgesellschaft Auf Aktien | Multiple enzyme granulates and their production |
WO2013007594A1 (en) | 2011-07-12 | 2013-01-17 | Novozymes A/S | Storage-stable enzyme granules |
US10711262B2 (en) | 2011-07-12 | 2020-07-14 | Novozymes A/S | Storage-stable enzyme granules |
EP2674476A1 (en) * | 2012-06-11 | 2013-12-18 | The Procter & Gamble Company | Detergent composition |
EP2674475A1 (en) * | 2012-06-11 | 2013-12-18 | The Procter & Gamble Company | Detergent composition |
WO2013188331A1 (en) * | 2012-06-11 | 2013-12-19 | The Procter & Gamble Company | Detergent composition |
CN104364364A (en) * | 2012-06-11 | 2015-02-18 | 宝洁公司 | Detergent composition |
RU2612142C2 (en) * | 2012-06-11 | 2017-03-02 | Дзе Проктер Энд Гэмбл Компани | Detergent composition |
US9752103B2 (en) | 2013-06-11 | 2017-09-05 | The Procter & Gamble Company | Detergent composition |
CN112980903A (en) * | 2021-03-11 | 2021-06-18 | 哈尔滨商业大学 | Microwave-assisted bio-enzyme catalytic reaction verification method |
CN112980903B (en) * | 2021-03-11 | 2023-02-28 | 哈尔滨商业大学 | Microwave-assisted bio-enzyme catalytic reaction verification method |
Also Published As
Publication number | Publication date |
---|---|
DK5593D0 (en) | 1993-01-18 |
FI953457A (en) | 1995-07-17 |
JPH08505526A (en) | 1996-06-18 |
FI953457A0 (en) | 1995-07-17 |
EP0680510A1 (en) | 1995-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2647695B2 (en) | Enzyme-containing granules | |
CN1312280C (en) | Process for preparing enzyme containing granule | |
KR100278498B1 (en) | Coated enzyme-containing granules | |
KR920004461B1 (en) | Enzyme containing granulates used as detergent additives | |
FI116849B (en) | New enzyme granules | |
JP4790957B2 (en) | Enzyme granule | |
EP0404806B1 (en) | Stabilized particulate composition | |
US5324649A (en) | Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof | |
EP0506791B1 (en) | Enzyme containing preparation and detergent containing such preparation | |
KR100413241B1 (en) | Enzyme-containing granules and method for producing the same | |
JP2002519052A (en) | New and improved enzyme-containing particles | |
JPH04503369A (en) | Detergent additive granules and their manufacturing method | |
EP0478684B1 (en) | Detergent additive granulate and detergent | |
CA2797032A1 (en) | Enzyme granules | |
JPS58179492A (en) | Granular enzyme for detergent and its preparation | |
US6413749B1 (en) | Granule containing protein and corn starch layered on an inert particle | |
US5858952A (en) | Enzyme-containing granulated product method of preparation and compositions containing the granulated product | |
US5376288A (en) | Detergent additive granulate and detergent | |
CN1742084B (en) | Stabilization of granules | |
WO1994016064A1 (en) | Enzyme containing granulate, method for production thereof, and use thereof | |
JP2003000234A (en) | Enzyme particle | |
JP2001157581A (en) | Method for producing conjugated enzyme granular agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR FI JP KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1994904998 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref country code: US Ref document number: 1995 481356 Date of ref document: 19950706 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 953457 Country of ref document: FI |
|
WWP | Wipo information: published in national office |
Ref document number: 1994904998 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1994904998 Country of ref document: EP |