AU641672B2 - Detergent additive granulate and detergent - Google Patents
Detergent additive granulate and detergentInfo
- Publication number
- AU641672B2 AU641672B2 AU59601/90A AU5960190A AU641672B2 AU 641672 B2 AU641672 B2 AU 641672B2 AU 59601/90 A AU59601/90 A AU 59601/90A AU 5960190 A AU5960190 A AU 5960190A AU 641672 B2 AU641672 B2 AU 641672B2
- Authority
- AU
- Australia
- 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.)
- Ceased
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
-
- 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
- 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
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)
Abstract
The detergent additive granulate is a cogranulate containing at least one enzyme and at least one photobleaching agent. If a detergent, a component of which is such detergent additive granulate, is used for laundering, the photobleaching agent will not tend to adhere selectively to the laundry during the initial washing process.
Description
DETERGENT ADDITIVE GRANULATE AND DETERGENT
The concept of incorporation of a photobleaching agent in a detergent is known, reference being made to e.g. DE 3430773, EP 119746, and EP 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. The introduction of photobleaching agents in detergents in solid form is not without problems, though. During the intial stages of the washing process, when the solid detergent agent is introduced into the washing float, 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. In case 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.
Thus, there is a need for a detergent additive in solid form comprising a photobleaching agent, whereby during the initial washing process the photobleaching agent will not tend to adhere selectively to the laundry.
Now, according to the invention it has been found that a detergent additive granulate of a special composition will fulfil the above objective.
Thus, the detergent additive granulate according to the invention is a co-granulate containing at least one enzyme and at least one photobleaching agent.
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).
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. In GB 2.179.053 an aqueous fabric washing detergent is described, which can contain both enzymes and a photobleaching agent. However, 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 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 spraydried, whereby the so-called base powder is formed. The enzyme which may optionally be added fvide page 4, line 29 in EP 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. Thus, the EP 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 28 13 198 describes a bleaching agent which contains a special photoactivator. This bleaching agent is produced by cogranulation of all constituents of the bleaching agent to a cogranulate 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 cogranulated.
The detergent additive granulate according to the invention can be produced by co-granulation in many ways, e.g. as indicated in the following.
I. A co-granulate of the so-called T-granulate type, as described in US
4,106,991 (Novo Nordisk A/S, Denmark), i.e. with cellulose fibres.
II. A co-granulate corresponding to US 4,661,452 (Novo Nordisk A/S, Denmark).
III. A co-granulate of the core type, as described in DK 4368/88. In this case it is specially preferred that the photobleaching agent is part of the core and that the enzyme is part of the coating.
IV. A co-granulate of the type described in DK 4369/88. In this case the photobleaching agent is added with the concentrated enzyme solution.
V. A co-granulate of the so-called "Marumerizer" type, as described in GB 1,362,365.
VI. A co-granulate of the prill type.
VII. A co-granulate of the Sparks type, as described in WO 85/05288.
VIII. A co-granulate of the fluid bed type.
In all cases the photobleaching agent is added as an aqueous solution, preferably as part of the granulation water.
In a preferred embodiment of the detergent additive granulate according to the invention the co-granulate is coated. In this manner the object of the invention is fulfilled to a very high extent. The usual coating agents may be used, e.g. the coating agents described in DK 0121/88, DK 1377/88, and DK 1378/88.
In a preferred embodiment of the detergent additive granulate according to the invention 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.
In a preferred embodiment of the 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
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.
Also, the invention comprises a detergent which contains the detergent additive granulate according to the invention. In a preferred embodiment of the detergent 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.
In the following the production of the detergent additive granulate is illustrated in Examples 1 - 11, and the use of the detergent addit e granulate is illustrated in Example 12.
EXAMPLE 1
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 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 celluloiytic activity, described in the document AF 187/3, and 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 Alle, 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 /tm and 900 μm 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 4.106.991 (Novo Nordisk A/S, Denmark).
By means of usual fluid bed techniques, 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.
EXAMPLE 2
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 Lodige 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.
EXAMPLE 3
A powder mixture containing a celluloiytic 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 ECCl Speswhite
0.60 kg of carbohydrate binder 8,85 kg of finely ground sodium sulphate
is transferred to a 50 liter Lδdige 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 4
1 kg of dry sifted (300-1000 μm) granulate produced as described in Example 2 is coated in a 5 liter Lodige mixer according to the method described in US 4,106,991 (Novo Nordisk A/S, Denmark), example 22.
Prep. 4A 1. coating layer 5.0% PEG 4000
2. coating layer 10.0% kaolin
3. coating layer 2.0% PEG 4000
Prep. 4B 1. coating layer 5.0% hydrogenated tallow
2. coating layer 10.0% kaolin
3. coating layer 2.0% hydrogenated tallow
Prep. 4C 1. coating layer 5.0% hydrogenated tallow
EXAMPLE 5
1 kg of dry sifted (300-1000 μm) granulate produced as described in Example 3 is coated as described in Example 4.
Prep. 5A 1. coating layer 5.0% PEG 4000
2. coating layer 10.0% kaolin
3. coating layer 2.0% PEG 4000
Prep. 5B 1. coating layer 5.0% hydrogenated tallow
2. coating layer 10.0% kaolin
3. coating layer 2.0% hydrogenated tallow
Prep. 5C 1. coating layer 4.0% hydrogenated tallow
EXAMPLE 6
A powder mixture containing a proteolytic enzyme and with the following composition
2.7 kg of SAVINASE* with an activity of 48.0 KNPU/g 3.0 kg of fibrous cellulose Arbocel BC 200
0.8 kg of kaolin ECCI Speswhite 1.4 kg of carbohydrate binder 11.2 kg of finely ground sodium sulphate
is transferred to a 50 liter Lodige mixer FM 50 and granulated with 5.3 kg of a granulation liquid made up by mixing of
3.1 kg of Tinolux BBS 0.4 kg of carbohydrate binder 0.2 kg of PVP K30 1.6 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 6.0 KNPU/g is obtained.
EXAMPLE 7
5.0 kg of base granulate produced as described in US 4,106,991 (Novo
Nordisk A/S, Denmark), example 1, except that it is based on sodium sulphate as the inert diluent, is provided with a photobleach containing layer by means of a fluidized bed spraying technique, as follows.
With simultaneous drying in a Glatt fluid bed coater of type WSG5 the 5 kg of base granulate is sprayed with an emulsion/suspension consisting of
0.75 kg of Tinolux BBS
0.50 kg of Bentonite ASB350 (ECCI)
0.25 kg of Glascol LS22P (Styrene-acrylic copolymer, 45% microemulsion, Allied Colloids)
2.00 kg of water,
and with proper selected air inlet and outlet temperature and atomizing air pressure that leaves every single enzyme granulate particle coated with a layer of dry Tinolux and bentonite with Glascol as the binding agent.
EXAMPLE 8
5 kg of a Tinolux/bentonite coated granulate produced as described in
Example 7 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 7.
EXAMPLE 9
5.0 kg of base granulate produced as described in US 4,106,991 (Novo Nordisk A/S), example 1, except that it is based on sodium sulphate as the inert diluent, is coated with a photobleach layer by means of a fluidized bed spraying technique.
With simultaneous drying in a Glatt fluid bed coater of type WSG5 the 5 kg of base granulate is sprayed with 0.75 kg Tinolux BBS with proper selected air inlet and outlet temperature and atomizing air pressure that leaves every single enzyme granulate particle coated with a layer of dry Tinolux photobleach.
EXAMPLE 10
5 kg of a Tinolux coated granulate produced as described in Example 9 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 EΞxample 7.
EXAMPLE 11
A powder composition containing an amylolytic enzyme and with the following composition is prepared for extrusion according to Example 4 in US 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). To obtain an extrudate with a string diameter of 0.8 mm the original Simon-Heesen pellet die with 8 mm holes is
equiped with a screen plate with 0.8 mm holes on the inside, which screen is supported by the die.
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 directly usable or it may be coated with a protective coating as described in example 22 of US 4,106,991 (Novo Nordisk A/S, Denmark) or in WO 89/08694 (Novo Nordisk A/S, Denmark) or in WO 89/08695 (Novo Nordisk A/S, Denmark).
Depending on formulation and extruder type products with particle shapes ranging from pure spheres to short rod like shapes can be produced. Methods for production of spheronized/marumerized products are described in GB 1,362,365 (Novo Nordisk A/S, Denmark) and US 4,661,452 (Novo Nordisk A/S, Denmark).
EXAMPLE 12
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.
Dosage of Tinolux 0.02%
Invention -
Prior art
Fluid bed granulate*) +
Dosage of Tinolux 0.04%
Invention ~
Prior art
Fluid bed granulate*) +
Legend: - absent spotting just detectable spotting -+ clearly detectable spotting + significant spotting
+ + very significant spotting
*) This prior art fluid bed granulate is produced by addition of the photobleach to a salt carrier in a fluidized bed.
Claims (6)
1. Detergent additive granulate which is a co-granulate containing at least one enzyme and at least one photobleaching agent.
2. Detergent additive granulate according to Claim 1, wherein the co-granulate is coated.
3. Detergent additive granulate according to Claim 1 or 2, wherein the enzyme is one or more of the enzymes protease, amylase, lipase, cellulase, oxidase and amidase.
4. Detergent additive granulate according to Claims 1 to 3, wherein between 2 and 40% w/w of cellulose fibres is incorporated into the granulate.
5. Detergent, which contains the detergent additive granulate according to Claims 1 - 4.
6. Detergent according to Claim 5, in which the concentration of the detergent additive granulate is between 0.05 and 5% w/w.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK3062/89 | 1989-06-21 | ||
DK306289A DK306289D0 (en) | 1989-06-21 | 1989-06-21 | DETERGENT ADDITIVE IN GRANULATE |
Publications (2)
Publication Number | Publication Date |
---|---|
AU5960190A AU5960190A (en) | 1991-01-08 |
AU641672B2 true AU641672B2 (en) | 1993-09-30 |
Family
ID=8118654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU59601/90A Ceased AU641672B2 (en) | 1989-06-21 | 1990-06-14 | Detergent additive granulate and detergent |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0478684B1 (en) |
JP (1) | JPH04506229A (en) |
KR (1) | KR920701410A (en) |
AT (1) | ATE98295T1 (en) |
AU (1) | AU641672B2 (en) |
BR (1) | BR9007470A (en) |
DE (1) | DE69005112T2 (en) |
DK (2) | DK306289D0 (en) |
EG (1) | EG19045A (en) |
ES (1) | ES2046788T3 (en) |
MX (1) | MX21242A (en) |
MY (1) | MY105995A (en) |
NZ (1) | NZ234159A (en) |
PT (1) | PT94439B (en) |
TR (1) | TR27368A (en) |
WO (1) | WO1990015856A1 (en) |
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 (en) * | 1993-01-18 | 1993-01-18 | Novo Nordisk As | GRANULES |
EP0763094A1 (en) * | 1994-05-31 | 1997-03-19 | Novo Nordisk A/S | Dye-transfer inhibitory preparation, and detergent composition comprising such a preparation |
US6410287B1 (en) | 1998-10-09 | 2002-06-25 | Kao Corporation | Enzyme particles |
DE19855677A1 (en) * | 1998-12-02 | 2000-06-08 | Henkel Kgaa | Production of detergent granules containing brighteners |
US6767882B1 (en) | 1999-06-21 | 2004-07-27 | The Procter & Gamble Company | Process for producing coated detergent particles |
AU5879900A (en) * | 1999-06-21 | 2001-01-09 | Procter & Gamble Company, The | Process for producing coated detergent particles |
IT1319655B1 (en) | 2000-11-15 | 2003-10-23 | Eurand Int | PANCREATIC ENZYME MICROSPHERES WITH HIGH STABILITY AND RELATIVE PREPARATION METHOD. |
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 |
HUE026168T2 (en) | 2007-02-20 | 2016-05-30 | Allergan Pharmaceuticals Int 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 |
CA2812862C (en) | 2010-10-01 | 2018-11-20 | Aptalis Pharma Limited | Enteric coated, low-strength pancrelipase formulations |
US9976171B2 (en) | 2011-08-08 | 2018-05-22 | 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 |
EP3157568A1 (en) | 2014-06-19 | 2017-04-26 | Aptalis Pharma Limited | 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 (en) * | 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/en not_active Application Discontinuation
-
1990
- 1990-06-14 JP JP2509933A patent/JPH04506229A/en active Pending
- 1990-06-14 DE DE90910607T patent/DE69005112T2/en not_active Expired - Fee Related
- 1990-06-14 BR BR909007470A patent/BR9007470A/en not_active Application Discontinuation
- 1990-06-14 EP EP90910607A patent/EP0478684B1/en not_active Expired - Lifetime
- 1990-06-14 KR KR1019910701466A patent/KR920701410A/en not_active Application Discontinuation
- 1990-06-14 AU AU59601/90A patent/AU641672B2/en not_active Ceased
- 1990-06-14 AT AT90910607T patent/ATE98295T1/en active
- 1990-06-14 ES ES199090910607T patent/ES2046788T3/en not_active Expired - Lifetime
- 1990-06-14 DK DK90910607.2T patent/DK0478684T3/en active
- 1990-06-14 WO PCT/DK1990/000149 patent/WO1990015856A1/en active IP Right Grant
- 1990-06-20 EG EG36690A patent/EG19045A/en active
- 1990-06-20 NZ NZ234159A patent/NZ234159A/en unknown
- 1990-06-20 MY MYPI90001045A patent/MY105995A/en unknown
- 1990-06-20 PT PT94439A patent/PT94439B/en not_active IP Right Cessation
- 1990-06-20 MX MX2124290A patent/MX21242A/en unknown
- 1990-07-17 TR TR00591/90A patent/TR27368A/en unknown
Also Published As
Publication number | Publication date |
---|---|
ATE98295T1 (en) | 1993-12-15 |
JPH04506229A (en) | 1992-10-29 |
MX21242A (en) | 1993-11-01 |
AU5960190A (en) | 1991-01-08 |
DK306289D0 (en) | 1989-06-21 |
PT94439B (en) | 1997-02-28 |
EP0478684B1 (en) | 1993-12-08 |
EG19045A (en) | 1994-12-30 |
DE69005112T2 (en) | 1994-04-14 |
ES2046788T3 (en) | 1994-02-01 |
MY105995A (en) | 1995-02-28 |
DK0478684T3 (en) | 1994-04-18 |
EP0478684A1 (en) | 1992-04-08 |
WO1990015856A1 (en) | 1990-12-27 |
TR27368A (en) | 1995-01-17 |
BR9007470A (en) | 1992-06-16 |
KR920701410A (en) | 1992-08-11 |
DE69005112D1 (en) | 1994-01-20 |
NZ234159A (en) | 1992-01-29 |
PT94439A (en) | 1991-02-08 |
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