DE69000662T2 - GRANULATE FROM DETERGENT ADDITIVES AND THE PRODUCTION THEREOF. - Google Patents

Abstract

The detergent additive granulate comprises a core with a primary detergent additive surrounded by a shell comprising a secondary detergent additive, a binder, and granulating agents, and optionally a filler, and a protective coating between the core and the shell, whereby the shell comprises cellulose fibres or artificial fibres, and whereby the core facultatively comprises cellulose fibres or artificial fibres. The detergent additive granulate exhibits a high physical strength, and the primary and secondary detergent additives are effectively separated from each other and/or from harmful environmental factors. The detergent additive granulate is produced by introduction of the components thereof into a granulating drum. This method of production is easily controllable and adapted for an industrial scale.

Description

This invention relates to a granulate of detergent additives and a process for its production.

The co-pending application WO-A 90/09440 (EP 0 458 849) of the same date describes and claims an enzyme-containing granulate with a core with a first enzyme and cellulose fibers or synthetic fibers in a proportion of between 1.5 and 40 wt.%, based on the weight of the core, surrounded by a shell comprising a binder, a filler and granulating agent and a secondary enzyme and a layer for sustained release between the core and the shell. Optionally, the shell also contains between 1.5 and 40 wt.% cellulose fibers or synthetic fibers.

The granulate according to the invention and its manufacturing process is a further development of the granulate and its manufacturing process described in EP-A-0 304 332, which is carried out in a drum granulator. It is understood that the term drum granulator represents a broad category of granulating devices, which include, for example, granulating discs and granulation mixers.

The enzyme-containing granulate described in EP-A-0 304 332 contains a core surrounded by a coating containing cellulose fibres or synthetic fibres in a proportion of 1.5 to 40% by weight, based on the dry weight of the granulate, excluding the core, a binder in a proportion of 0 to 15% by weight, based on the dry weight of the granulate, excluding the core except for a filler, and one or more granulating agents, wherein the core and/or the coating contains an enzyme.

The invention is a further development of the particular embodiment of the invention described in EP-A-0 304 332 which contains an enzyme either in the core or in the shell. However, in the detergent additive granules of the invention, the shell or core does not necessarily contain an enzyme; rather, the core contains a detergent additive (which may be an enzyme, referred to herein as the primary detergent additive) and the shell contains another detergent additive (which may still be an enzyme, referred to herein as the secondary detergent additive). In cases where the first detergent additive should be protected from the second detergent additive and/or environmental influences, e.g. in cases where an enzyme is weakened by a bleach and moisture in the atmosphere, or vice versa, an effective separation between the first and second detergent additives is needed during storage. What is also needed is a granulate with high physical strength and a corresponding manufacturing process that can be easily controlled and adapted to an industrial scale.

Therefore, the purpose of the invention is to provide a granulate of detergent additives with a high physical strength, containing a primary and a secondary detergent additive of the type mentioned above, the primary and secondary detergent additives being effectively separated from each other and/or from harmful environmental influences, and to provide a corresponding manufacturing process which is easily controllable and adapted to an industrial scale.

The detergent additive granulate according to the invention contains a core with a primary detergent additive, which is surrounded by a shell containing a secondary detergent additive, a binder and granulating agent, and optionally a filler, and a protective coating between core and shell, wherein the shell contains cellulose fibers or synthetic fibers, preferably in a proportion of between 1.5 and 40% by weight of the shell, preferably between 5 and 20% by weight of the shell, and wherein the core optionally contains cellulose fibers or synthetic fibers, preferably in an amount of between 1.5 and 40% by weight of the core, more preferably between 5 and 20% by weight of the core.

US Patent No. 4,740,469 describes enzyme granules containing synthetic fibers coated with a wax material and a finely divided dye. However, in contrast, the detergent additive granules of the present invention comprise a shell containing a secondary detergent additive and cellulose fibers or synthetic fibers.

Due to the protective coating between core and shell, the two detergent additives do not harm each other during storage and only when used during washing are the two detergent additives brought into contact with each other. Also, the physical strength of the granules is high due to the content of cellulose fibers or synthetic fibers in the shell. Furthermore, it has been surprisingly found that the manufacturing process by granulation, carried out according to the guidelines given in US Patent No. 4,106,991, which is set out in EP-A-0 304 332 cited above, can be easily controlled even with two non-enzymatic detergent additives and can be easily adapted to an industrial scale.

EP 0 268 773 describes encapsulated enzymes which are used in some respects are similar to the granules of detergent additives according to the invention in their broadest form. However, the encapsulated enzymes of the prior art do not contain reinforcing cellulose fibers or synthetic fibers in the sheath and are not produced by the granulation process described above, but by the fluidized bed process, which is not well adapted to production on an industrial scale.

The protective coating may be any protective coating used in the art that does not harm the primary or secondary detergent additive or otherwise interfere with the manufacturing process or application of the granules. Examples of protective coatings that can be used are: fatty acid esters, alkoxylated alcohols, polyvinyl alcohols, ethoxylated alkylphenols, polyethylene glycols (molecular weight 1000 to 8000), linear alcohol copolymers (molecular weight 1450 to 2670), polyvinylpyrrolidone (molecular weight 26000 to 33000), polymeric nonylphenyl ethoxylates (molecular weight 1975 to 4315) and dinonylphenyl ethoxylate (average molecular weight 6900), fatty acids, e.g. palmitic acid, stearic acid and arachidonic acid, paraffins, beeswax, waxes, mono-, di- or triglycerides of simple fatty acids or mixed fatty acids, fatty alcohols, methylcellulose, ethylcellulose, hydroxypropylcellulose and coconut monoethanolamide.

Examples of pairs of a primary and secondary detergent additive are the following: (optical brightener)-(enzyme), (enzyme)-(optical brightener), (enzyme)- (bleach activator), (bleach activator)-(enzyme), (bleach activator)- (optical brightener), (optical brighteners)-(bleach), (enzyme)-(chlorine cleaner), (bleach activator)-(chlorine cleaner), (optical brighteners)-(chlorine cleaner), (bleach)-(enzyme), and (enzyme)-(bleach).

In a preferred embodiment of the granulate according to the invention, the core has a shape corresponding to a maximum ratio between the largest and the smallest dimension of about 3, preferably about 2, more preferably about 1.5. In this embodiment, a satisfactory coating can always be obtained around the core.

In a preferred embodiment of the granulate according to the invention, the proportion of the core is between 5 and 85% by weight, preferably between 10 and 50% by weight of the granulate, more preferably between 15 and 40% by weight of the granulate. If the proportion of the core is above 85%, loading with a sufficient proportion of the secondary detergent additive becomes difficult, and if the proportion of the core is less than 5%, loading with a sufficient proportion of the primary detergent additive becomes difficult.

In a preferred embodiment of the granulate according to the invention, the core has an average particle size between 100 and 1000 μm, preferably 200 to 700 μm. These are the particle sizes most frequently required by users.

In a preferred embodiment of the granulate according to the invention, the core or the shell contains an enzyme. An enzyme is a typical detergent additive that provides protection against aggressive detergent components.

In a preferred embodiment of the granulate according to the invention, the enzyme is a protease, an amylase, a lipase, an amidase, a cellulase or an oxidase. These are the most common enzymes for industrial detergent purposes.

In a preferred embodiment of the granulate according to the invention, the filler consists of or comprises inorganic Salts. This produces inexpensive granules.

In a preferred embodiment of the granulate according to the invention, the shell is surrounded by a final dust-suppressing coating. This is advantageous in cases where the shell tends to generate an unacceptable amount of dust. This final dust-suppressing coating can also serve as a further protective coating in certain cases.

In a preferred embodiment of the granulate according to the invention, the protective coating is a mixture of a mono- and diglyceride of a fatty acid. It has been found that in this embodiment a highly satisfactory protective effect can be obtained during storage. Mixtures of the type described in EP-A-0 304 332 can be used advantageously.

In a preferred embodiment of the granulate according to the invention, the protective coating contains an antioxidant.

Suitable examples of antioxidants or reducing agents are thiosulfates, sulfites, hydrogen sulfites, ascorbic acid, ascorbates or butylhydroxytoluene. In many cases, even better storage stability can be achieved due to the presence of the antioxidant.

The invention also includes a manufacturing process for the granulate according to the invention.

The process according to the invention for the production of the granules of detergent additives comprises introducing the core into a granulating drum, whereupon the protective coating material, the sheath material and optionally a material for the final dust-suppressing coating, and further cellulose fibers or synthetic fibers in the appropriate amounts and introduced into the granulating drum at the appropriate stages.

It is understood that any granulating drum can be used in connection with the process of the invention. The entire process can be carried out in one of these granulating drums. It is also understood that the core can be coated with the protective coating material in one granulating drum, after which the coated core can be separated and passed on to another granulating drum for application of the jacket, after which, if desired, the application of a dust suppressing coating can be carried out in the same granulating drum or another granulating drum.

The process according to the invention can be carried out both batchwise and continuously.

The invention is illustrated by the following examples.

The activity units used in the examples are defined as follows. Enzyme Activity Unit Definition given in proteolytic amylolytic lipolytic Anson

These freely available AF publications can be obtained upon request from NOVO NORDISK A/S, Novo Allé, 2880 Bagsvaerd, Denmark.

Manufacturing examples EXAMPLE 1

15 kg of a powder mixture with the formulation:

15% fiber cellulose, ARBOCEL BC 200

15% optical brightener, TINOPAL DMS-X conc. CIBA GEIGY

4% Kaolin SPESWHITE ECC

12% carbohydrate binder

54% finely ground sodium sulfate

are granulated in a Lödige mixer FM 50 with pure water as granulating agent as described in US Patent No. 4,106,991, Example 1.

The granules are dried in a fluid bed to a water content below 1% and finally sieved to obtain a product with a particle range of 300 µm to 900 µm.

EXAMPLE 2

7 kg of a granulate prepared as in Example 1 with a particle size range between 300 and 900 µm are coated with a layer of glycerol stearate/palmitate Grindtek MSP 90 (melting point 68ºC) and bentonite ASB 350 ECC in the following manner.

The granules are heated to 75-80ºC in a thermally insulated 20 l Lödige mixer, the temperature of which is kept constant throughout the coating process. The heated granules are mixed and sprayed with 700 g of molten MSP90, followed by dusting with 1000 g of bentonite, followed by dusting with 210 g of MSP90, followed by dusting with 1000 g of MSP90, followed by spraying with 210 g of MSP90.

The granules are finally cooled to room temperature in a fluid bed and sieved to between 300 and 1000 um.

EXAMPLE 3

A granulate having an inner core containing an optical brightener and an outer shell containing a proteolytic enzyme, the core and the shell being separated by a protective layer, is prepared in the following manner.

6 kg of a sheath material with the composition:

2.5 kg SAVINASE conc. with proteolytic activity 37 KNPU/g

0.5 kg fibre cellulose ARBOCEL BC 200

0.6 kg carbohydrate binder

0.2 kg Kaolin SPESWHITE ECC

1.2 kg finely ground sodium sulfate

are mixed and applied in layers to the surface of 8 kg of granules prepared as described in Example 2, in a manner as described in Danish Patent No. 157937, Example 1, except that in the present example the core contains an optical brightener and that a 50 l Lödige mixer FM 50 was used.

The granules are finally dried to a water content below 1% and sieved between 300 and 1000 μm.

The granules have a proteolytic activity of 6.0 KNPU/g.

EXAMPLE 4

7 kg of a granulate prepared as described in Example 3 are coated with a layer of sodium thiosulfate and kaolin by a conventional fluidized bed coating process.

280 g sodium thiosulfate and 280 g kaolin SPESWHITE ECC are dissolved/dispersed in 1000 g water and sprayed onto the 7 kg granulate in a Glatt WSG 5 fluid bed with continuous layering and drying.

Air inlet temperature 50ºC. Air outlet temperature 35ºC.

The process is completed with a 5 minute drying period at an inlet air temperature of 50ºC.

The granules have a proteolytic activity of 5.2 KNPU/g.

EXAMPLE 5

7 kg of a granulate prepared as described in Example 4 are coated with a protective coating of 280 g Grindtek MSP90, followed by 875 g titanium dioxide: kaolin (SPESWHITE) 1:1, followed by 140 g Grindtek MSP 90, as described in Example 2.

The granules are cooled to room temperature in a fluid bed and sieved to between 300 and 1000 μm.

The granules have a proteolytic activity of 4.7 KNPU/g.

Stability test of granules in examples 3, 4 and 5

The stability test is carried out at a temperature of 37ºC and a humidity of 70%. Days trial restact.

The above data demonstrates that the final dust suppressing and protective coating produces increased stability.

EXAMPLE 6

14.7 kg of a powder mixture with the composition

2.2 kg fiber cellulose, ARBOCEL BC 200

1.2 kg Bentonite, ASB350, ECC

1.8 kg carbohydrate binder

9.5 kg TAED

were granulated in a Lödige mixer FM 50 with 3.0 kg of a 2% aqueous solution of a carbohydrate binder as described in US Patent No. 4,106,991, Example 1.

In a fluidized bed, the granules were mixed to a water content dried below 1% and finally sieved to obtain a product with a particle range of 300 μm to 900 μm.

10 kg of a dry 300-900um product was subsequently coated with 8.0% hydrogenated tallow (melting point 59ºC) and 28% kaolin, SPESWHITE ECC, in the manner described in Example 2, except that the tallow was applied in a single (first) step followed by dusting with kaolin.

A granule having an inner core containing TAED and an outer shell containing a proteolytic enzyme, the core and shell being separated by a protective layer, was prepared in the following manner.

10 kg of the tallow-coated granules containing TAED were cooled to room temperature and then brought to a Lödige mixer FM 50 and sprayed with 200 g PEG 300 in a first step, followed by layering of 4.6 kg of a mixture of sheath material mixture with the composition

0.6 kg SAVINASE concentrate, 50 KNPU/g

0.5 kg fiber cellulose, Arbocel BC200

0.2 kg titanium dioxide

0.3 kg Kaolin, SPESWHITE ECC

0.2 kg carbohydrate binder

2.8 kg finely ground sodium sulfate

The shell was coated with 1.4 kg of a 28.5% aqueous solution of a carbohydrate binder as described in Danish Patent 157937, Example 1, except that in the present example the core contains a perborate activator, TAED, and that a 50 l Lödige mixer was used.

The granules were finally dried to a water content below 1% and sieved between 300 μm and 1000 μm.

EXAMPLE 7

A TAED-containing hydrogenated tallow coated granule was prepared as described in Example 6, except that 20% kaolin was used in the wax coating step.

A granulate having an inner core containing TAED and an outer shell containing an optical brightener, the core and shell being separated by a protective layer, was prepared in the following manner.

10 kg of the tallow-coated granules containing TAED were cooled to room temperature and then brought to a Lödige mixer FM 50 and sprayed with 200 g PEG 300 in a first step, followed by layering of 4.6 kg of the sheath material mixture with the composition

0.75 kg optical brightener, Tinopal DMS-X, Ciba-Geigy

0.75 kg fiber cellulose, Arbocel BC200

0.20 kg titanium dioxide

0.30 kg Bentonite ASB 350, ECC

0.20 kg carbohydrate binder

2.40 kg finely ground sodium sulphate

The shell was fed by a continuous, weight loss self-regulating powder dosing system with a powder dosing rate of 20 kg/h. A total of 1.4 kg of a 28.5% aqueous carbohydrate binder solution was sprayed to bind the powder to the surface of the core particles. Otherwise, the coating was applied as described in PCT WO 89/08695, Example 1.

The granules were finally dried to a water content below 1% and sieved to obtain a product with a particle range from 300 to 900 to receive.

EXAMPLE 8

10 kg of a SAVINASE granulate with particle sizes between 300 µm and 700 µm, prepared as described in US 4,106,991, Example 1, except that it was based on sodium sulfate, were coated with 8% hydrogenated tallow and 26% kaolin as described in Example 6.

A granulate with an inner core containing the proteolytic enzyme SAVINASE and an outer shell containing an optical brightener, the core and the shell being separated by a protective layer, was prepared in the following manner.

10 kg of the tallow-coated granules containing SAVINASE were cooled to room temperature and then taken to a Lödige mixer FM 50 and sprayed with 200 g PEG 300 in a first step, followed by layering of 9.2 kg of a sheath material mixture with the composition

1.5 kg optical brightener, Tinopal DMS-X, Ciba Geigy

1.0 kg fiber cellulose, Arbocel BC200

0.4 kg titanium dioxide

0.6 kg Kaolin, SPESWHITE ECC

0.4 kg carbohydrate binder

5.3 kg finely ground sodium sulfate

The shell was fed by means of a continuous, weight loss self-regulating powder dosing system with a powder dosing rate of 20 kg/h and with a total of 2.6 kg of a 26.2% aqueous carbohydrate binder solution, and otherwise as described in PCT WO 89/08695, Example 1.

The granules were finally dried to a water content below 1% and sieved to obtain a product with a particle range of 300 to 900 µm.

EXAMPLE 9

10 kg of a SAVINASE® granulate having a particle range between 300 µm and 1000 µm, prepared as described in US 4,106,991, Example 1, except that it was based on sodium sulfate, were coated with 10% hydrogenated talc and 30% kaolin as described in Example 6.

A granulate with an inner core containing the proteolytic enzyme SAVINASE and an outer shell containing a chlorine cleaner, the core and shell being separated by a protective layer, was prepared in the following manner.

10 kg of the tallow-coated granules containing SAVINASE were brought to a Lödige mixer FM 50 at 60ºC and maintained at this temperature during the coating process using 60ºC hot water in the heating jacket of the mixer.

9.2 kg of sheath material with the composition

6.8 kg ammonium sulphate

1.0 kg fibre cellulose, Arbocel BC 200

0.2 kg titanium dioxide

0.7 kg Kaolin, SPESWHITE ECC

0.5 kg carbohydrate binder

were tested using a continuous, weight loss self-regulating powder dosing system with a powder dosing rate of 50 kg/h and a total of 2.1 kg of 34.7% Carbohydrate binder solution was added (the binder solution was slightly acidified with 0.7% citric acid to suppress ammonia evaporation or the ammonia odor during granulation). Otherwise, the coating was applied as described in PCT WO 89/08695, Example 1.

The granules were finally dried to a water content below 1% and sieved to obtain a product with a particle range of 300 to 1000 µm.

EXAMPLE 10

10 kg of a SAVINASE® granulate having a particle range between 300 µm and 1000 µm, prepared as described in US 4,106,991, Example 1, except that it was based on sodium sulfate, were coated with 5% hydrogenated talc and 15% kaolin as described in Example 6.

A granulate having an inner core containing the proteolytic enzyme SAVINASE and an outer shell containing a chlorine cleaner, the core and shell being separated by a protective layer, was prepared in the manner described in Example 9.

EXAMPLE 11

10 kg of a SAVINASE granulate with a particle range between 300 µm and 1000 µm, prepared as described in US 4,106,991, Example 1, except that it was based on sodium sulfate, were coated with 3% hydrogenated talc and 10% kaolin as described in Example 6.

A granulate having an inner core containing the proteolytic enzyme SAVINASE and an outer shell containing a chlorine cleaner, the core and the shell being separated by separated by a protective layer was prepared in the manner described in Example 9.

EXAMPLE 12

10 kg of an ALCALASE® granulate having a particle range between 300 µm and 1000 µm, prepared as described in US 4,106,991, Example 1, except that it was based on sodium sulfate, were prepared with 5% hydrogenated fatty acid (melting point 58ºC) and 16% kaolin as described in Example 6.

A granulate with an inner core containing the proteolytic enzyme ALCALASE and an outer shell containing a chlorine cleaner, the core and shell being separated by a protective layer, was prepared in the following manner.

10 kg of the tallow-coated granules containing ALCALASE were brought to a Lödige mixer FM 50 at 60ºC and maintained at this temperature during the coating process using 60ºC hot water in the heating jacket of the mixer.

9.2 kg of sheath material with the composition

7.0 kg ammonium sulphate

1.0 kg fiber cellulose, Arbocel BC200

0.7 kg Kaolin, SPESWHITE ECC

0.5 kg carbohydrate binder

were applied as described in Example 9.

The granules were finally dried to a water content below 1% and sieved to obtain a product with a particle range of 300 to 1000 µm.

Washing tests with granules from examples 9, 10 and 11

Test: Washing test with granules containing chlorine cleaners

Principle: Terg-O-tometer, 100 rpm

Water: 6º dH (33% tap water, 67% deionized water)

Temperature: 40ºC

Time: 15 min. After 15 min of washing, Na₂S₂O₃ is added to all beakers (over a period of 14 min). Then the fabric samples are rinsed.

Detergent: 1 g/l US base powder

pH: Measured at: 9.2

Textile/liquid ratio: 8 swatches/800 ml (the dimensions of each swatch are 7 x 7 cm)

Rinse: 10 + 15 min under running tap water

Test material: Pre-rinsed grass on cotton

Enzymes: Savinase (Ref) 7.04 KNPU(S)/g Savinase granules, Ex. 9 3.84 -Savinase granules, Ex. 10 4.40 -Savinase granules, Ex. 11 4.61 -

Enzyme dosage: 0 - 0.09 KNPU/l

Hypochlorite dosage: 0 - 4.5 - 9.0 ppm NaOCl

Repetitions : 2 independent repetitions

Analysis: % remission at 460 nm on Elrepho 2000 (+UV)

Remarks: The detergent is dissolved and heated to 40ºC in the Terg-O-tometer. NaOCl, enzyme and test sample are added in the order given within 60 seconds. Results: Enzyme dosage Savinase

Remarks:

Without hypochlorite dosage, practically exactly the same enzyme action is observed for the four granules, measured by R. At a dosage of 4.5 ppm hypochlorite, the effect of the reference Savinase is reduced to approximately half the effect, measured by Δ, while the three granules from the examples still show maximum effect. At the high dosage of hypochlorite, no enzyme action of significance is observed with respect to the reference. The granule from example 9 still shows approximately 50% effect due to the high dosage of tallow, which slows down the dissolution rate, combined with the chloric acid detergent.

Claims (17)

1. Granules of detergent additives comprising a core containing a primary detergent additive surrounded by a shell containing a secondary detergent additive, a binder and granulating agent, and a protective coating between core and shell, the shell comprising cellulose fibers. 2. Granules of detergent additives according to claim 1, characterized in that the shell comprises a filler. 3. Granules of detergent additives according to claims 1 to 2, characterized in that the cellulose fibers in the coat are present in an amount of between 1.5 and 40% by weight of the coat. 4. Granules of detergent additives according to claim 3, characterized in that the cellulose fibers are present in the casing in an amount of between 5 and 20% by weight of the casing. 5. Granules of detergent additives according to claim 4, characterized in that the core comprises cellulose fibers or synthetic fibers. 6. Granules of detergent additives according to claim 5, characterized in that the cellulose fibers or synthetic fibers are present in the core in an amount of between 1.5 and 40 wt.% of the core. 7. Granules of detergent additives according to claim 6, characterized in that the cellulose fibers or synthetic fibers are present in the core in an amount of between 5 and 20 wt.% of the core. 8. Granules according to claims 1 to 7, characterized in that the core has a shape corresponding to a maximum ratio between the largest and the smallest dimension of approximately 3, preferably approximately 2, more preferably approximately 1.5. 9. Granules according to claims 1 to 8, characterized in that the proportion of the core is between 5 and 85% by weight, preferably between 10 and 50% by weight of the granules, most preferably between 15 and 40% by weight of the granules. 10. Granules according to claims 1 to 9, characterized in that the core has an average particle size of between 100 and 1000 µm, preferably 200 to 700 µm. 11. Granules according to claims 1 to 10, characterized in that the core or the shell contains an enzyme. 12. Granules according to claims 1 to 11, characterized in that the enzyme is a protease, an amylase, a lipase, an amidase, a cellulase and/or an oxidase. 13. Granules according to claims 1 to 12, characterized in that the filler consists of or contains inorganic salts. 14. Granules according to claims 1 to 13, characterized in that the casing is surrounded by a final dust-suppressing coating. 15. Granules according to claims 1 to 14, characterized in that the protective layer is a mixture of a mono- and diglyceride of a fatty acid. 16. Granules according to claims 1 to 15, characterized in that the protective layer contains an antioxidant. 17. A process for producing the granulate of detergent additives according to claims 1 to 16, which comprises introducing the core into a granulating drum, whereupon the protective coating agent, the shell material, and optionally an agent for a final dust-suppressing coating and further cellulose fibers or synthetic fibers are introduced into the granulating device in the appropriate amounts and in the appropriate stages in sequence.