NZ234159A

NZ234159A - Detergent additive granulate containing enzyme and photobleaching agent

Info

Publication number: NZ234159A
Application number: NZ234159A
Authority: NZ
Inventors: Per Falholt; Erik Kjaer Markussen
Original assignee: Novo Nordisk As
Priority date: 1989-06-21
Filing date: 1990-06-20
Publication date: 1992-01-29
Also published as: DK0478684T3; DK306289D0; EP0478684A1; PT94439A; KR920701410A; WO1990015856A1; ATE98295T1; JPH04506229A; EG19045A; AU5960190A; ES2046788T3; MX21242A; AU641672B2; BR9007470A; PT94439B; MY105995A; TR27368A; DE69005112D1; DE69005112T2; EP0478684B1

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

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £34159 234 159 Specification Fiie*.': ..3v0..r..Co.n30. ,d. I, l.Ci A. ;I L : ;•i^.aiiinon Daie: ... JAN.,B9Z.. ;P.O. Jounia!, No: ;tyQ 0PA ;Patents Form No. 5 ;NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION ;DETERGENT ADDITIVE GRANULATE ;WE, NOVO NORDISK A/S, a Danish joint-stock company of Novo Alle, 2880 Bagsvaerd, DENMARK ;hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: ;- 1 - ;(followed by page la) ;. - ia - 23415 ;0^ This invention relates to a detergent additive in granulate form that contains an enzyme and a photobieaching agent. The invention also relates to detergents that contain the additive. ;The concept of incorporation of a photobieaching agent in a detergent is known, reference being made to e.g. DE 3430773, EP 119746, and EP 87833. The photobieaching agent is inactive if not exposed to UV light, and 5 thus, under normal conditions, the photobieaching 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 wiil function as a bleaching agent already in the washing solution and thus damage sensitive detergent additives, especially enzymes. ;10 The introduction of photobieaching 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 photobieaching agent or particles of detergent additives, which contains photobieaching agents at the surface thereof, will tend to adhere to the laundry 15 due to a selective adhesion ability of the photobieaching agent to the laundry, and also such photobieaching agent will tend to stay with the laundry without being dissolved during the washing process. Most photobieaching agents possess a very intense color, and such photobieaching agents will create a most undesirable staining of the laundry. In case the photobieaching agent is colorless, the above 20 indicated attachment thereof to the laundry during the washing process will create an uneven concentration of photobieaching 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 25 comprising a photobieaching agent, whereby during the initial washing process the photobieaching agent wiil 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 wiil fulfil the above objective. ;Therefore this invention provides a detergent 3C additive granulate which is a co-granulate containing at least one enzyme and at least one photobieaching agent. ;[ N.Z. PATr* OFFICE 3311.200 - 19SC-06-12. N8/NPu 29 OCT 1991 2 3 4 1 5 2 The photobieaching agent can be any photobieaching 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 5 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 photobieaching agent. 10 In GB 2.179.053 an aqueous fabric washing detergent is described, which can contain both enzymes and a photobieaching 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. 15 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 20 may optionally be added (vide 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, photobieaching agent containing particles and 25 photobieaching 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 30 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 photobieaching agent, and cogranulated. 3311.200 - 199006-12. NB/NRu 234159 a 3 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 4,106,391 (Novo Ncrdisk A/S, Denmark), i.e. with cellulose fibres. 5 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 European application ' 0 304 332. In this case it is specially preferred that the photobieaching agent is part of the core and that the enzyme is part of the coating. 10 IV. A co-granulate of the type described in US patent 4876198. In this case the photobieaching 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. 15 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 photobieaching agent is added as an aquecus solution, preferably as part of the granulation water. In a preferred embodiment cf the detergent additive granulate according 20 to the invention the co-granulate is coated. In this manner the object of the invention is fulfilled to a very high extent. Tne usual coating agents may be used, e.g. the coating agents described in us patent 4973417, to 89/08694 and European application 0 404 806. In a preferred embodiment of the detergent additive granulate according to the invention the enzyme is one or more y£_the enzymes protease, amylase, N.Z. PAT.TNT OFFICE 3311.200 • 199006-12. N8/NRu oo opt loot . 234 159 4 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 5 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. 10 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 photobieaching effect is fully satisfactory. In the following the production of the detergent additive granulate is 15 illustrated in Examples 1-11, and the use of the detergent additive granulate is illustrated in Example 12. EXAMPLE 1 A powder mixture containing a proteolytic enzyme and with the following composition 20 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 25 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 3311.200 - 1990-06-12, NB/NRu 5 2341 5 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-G3, KLU is an activity unit for lipolytic activity, described in the 5 document AF 95/5, CSU is an activity unit for cellulolytic 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 the New Zealand Patent Office or from Novo Nordisk, Novo Alle DK-2880 Bagsvaerd, Denmark. 10 Tinclux B8S is a photobieaching agent, which is a derivative or tetrabenzo-tetraazacorphine. Tne moist granulate is dried on a fluid bed to a water content below 1%, and the sieve fraction of the granulate between 3C0 nm and SCO is taken out as a product. This product is coated with 3.2% of polyethylene glycol (PEG CCO) 15 and 10% of kaolin (Speswhite, ECC) by means of the method described in Example 22 in US 4.1C6.991 (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 hydroxyprcpyl cellulose. 20 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 Arbocei BC 2CO 25 1.50 kg of bentonite ECCI ASS350 Tne final preparation exhibited a proteolytic activity of 5.7 KNPU/g. 0.S0 kg of carbohydrate binder 8,90 kg of finely ground sodium sulphate 3311.200 • 1990-06-12. N8/NRu 6 234 159 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 5 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. 10 EXAMPLE 3 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 15 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 Lodige mixer FM 50 and granulated with 3.4 kg of a granulation liquid made up by mixing of 20 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. 25 The granulate is dried and sifted as described in Example 1. 3311.200 - 1990-06-12, NB/NRu 234 159 EXAMPLE 4 1 kg of dry sifted (300-1000 /xm) 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. 5 Prep. 4A 1. coating layer 2. coating layer 3. coating layer 5.0% PEG 4000 10.0% kaolin 2.0% PEG 4000 Prep. 4B 10 1. coating layer 2. coating layer 3. coating layer 5.0% hydrogenated tallow 10.0% kaolin 2.0% hydrogenated tallow Prep. 4C 1. coating layer 5.0% hydrogenated tallow EXAMPLE 5 1 kg of dry sifted (300-1000 /im) granulate produced as described in Example 3 is coated as described in Example 4. 15 Prep. 5A 1. coating layer 2. coating layer 3. coating layer 5.0% PEG 4000 10.0% kaolin 2.0% PEG 4000 Prep. 5B 20 1. coating layer 2. coating layer 3. coating layer 5.0% hydrogenated tallow 10.0% kaolin 2.0% hydrogenated tallow Prep. 5C 1. coating layer 4.0% hydrogenated tallow 3311.200- 199CH36-12, NB/NRu 23 4 1 5 8 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 5 3.0 kg of fibrous cellulose Arbocel BC 200 0.8 kg of kaolin ECCI Speswhite I.4 kg of carbohydrate binder II.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 10 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 15 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 20 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. 3311.200-199006-12, NB/NRu 9 234159 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) 5 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 10 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 15 100 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 20 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. 3311.200 - 199006-12, NB/NRu 23 4 1 5 9 10 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. 5 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 10 300 g of Glascol LS22P (45% microemulsion) 1000 g of water by means of the same fluidized bed coating technique as described in Example 7. EXAMPLE 11 A powder composition containing an amylolytic enzyme and with the 15 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 20 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 3311.200- 1990-06-12, NB/NRu 11 2 3 4 1 5 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 5 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 10 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 15 (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). 20 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. 25 The spotting from the granules on the white textile is evaluated after 1 minute according to the grades shown in the legend. 3311.200 • 1990-06-12, NB/NRu </div>

Claims

<div class="application article clearfix printTableText" id="claims"> ■ ■"> ■" '=• ,v- •; • ,;^¥*.,.,,, _, 12 234 Dosage of Tinolux 0.02% Invention Prior art Fluid bed granulate*) + 5 Dosage of Tinolux 0.04% Invention Prior art Fluid bed granulate*) + Legend: 10 -- absent spotting just detectable spotting -+ clearly detectable spotting + significant spotting + + very significant spotting 15 *) This prior art fluid bed granulate is produced by addition of the photobleach to a salt carrier in a fluidized bed. 3311.200 - 1990-06-12, NB/NRu 234159 13 WHAT WE CLAIM IS

1. A detergent additive granulate which is a co-granulate containing at least one enzyme and at least one photobieaching agent.

2. A detergent additive granulate according to claim 1, wherein the co-granulate is coated.

3. A detergent additive granulate according to claim 1 or 2, wherein the enzyme is selected from one or more of protease, amylase, lipase, cellulase, oxidase and amidase.

4. A detergent additive granulate according to any one of claims 1 to 3 further comprising from 2 to 40% w/w of cellulose fibre that is incorporated into the granulate.

5. A detergent additive granulate according to any one of claims 1 to 4 in which the photobieaching agent is zinc phthalocyanine sulfonate, a tetrabenzo-tetraazaporphine derivative or aluminium phthalocyanine sulfonate.

6. A detergent additive granulate according to any one of claims 1 to 5 that is produced in a drum granulator.

7. A detergent additive granulate according to claim 1 and substantially as described in this specification with reference to any one of examples 1 to 11.

8. A detergent which contains the detergent additive granulate according to any one of claims 1 to 7.

9. A detergent according to claim 8, in which the concentration of the detergent additive granulate is between 0.05 and 5% w/w BALDWIN, SON S CAREY </div>