COATINGS OF ENZYME PARTICLES COMPRISING ORGANIC WHITE PIGMENTS

Abstract

The present invention relates to novel enzyme particles comprising a core and a coating, wherein the core comprises at least one enzyme and the coating comprises at least one organic white pigment and uses thereof.

Claims

1. An enzyme particle comprising a core and a coating, wherein the core comprises at least one enzyme and the coating comprises at least one organic white pigment.

2. The enzyme particle according to claim 1, wherein the enzyme particle is in the form of an enzyme granule.

3. The enzyme particle according to claim 1, wherein the at least one organic white pigment is comprised in the coating in the range of from 10 to 90 wt.-%, based on the total weight of the coating.

4. The enzyme particle according to claim 1, wherein the at least one organic white pigment is in the form of hollow organic particles.

5. The enzyme particle according to claim 1, wherein the at least one white pigment is based on polymers, comprising nonionic ethylenically unsaturated monomers.

6. The enzyme particle according to claim 5, wherein the nonionic ethylenically unsaturated monomer is selected from the group consisting of styrene, acrylonitrile, methacrylamide, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, or mixtures thereof.

7. The enzyme particle according to claim 1, wherein the at least one organic white pigment is based on emulsion polymer particles, obtainable by a process for preparing emulsion polymer particles comprising: a) providing an aqueous emulsion of i) multi-stage emulsion polymer, comprising a core stage polymer and a sheath stage polymer, wherein the core stage polymer comprises, as polymerized units, from 5 to 100 percent by weight, based on the weight of the core stage polymer, of hydrophilic ethylenically unsaturated monomer, and from 0 to 95 percent by weight, based on the weight of the core stage polymer, of at least one nonionic ethylenically unsaturated monomer; and wherein the sheath stage polymer comprises, as polymerized units, at least 50 percent by weight of nonionic ethylenically unsaturated monomer; ii) monomer at a level of at least 0.5 percent by weight based on the weight of the multi-stage emulsion polymer; and iii) swelling agent; and b) reducing the level of monomer by at least fifty percent.

8. The enzyme particle according to claim 1, wherein the at least one organic white pigment consists of at least one hollow organic particle, based on emulsion polymer particles, obtainable by sequential polymerization, comprising polymerizing in a sequential polymerization i) a seed, and ii) then reacting with a swell-seed comprising 55 to 99.9 wt.-% of one or more nonionic ethylenically unsaturated monomer and 0.1 to 45 wt.-% of one or more ethylenically unsaturated hydrophilic monomer, all based on an overall weight of a core stage polymer comprising both seed and swell-seed, iii) then polymerizing a first shell comprising 85 to 99.9 wt.-% of one or more than nonionic ethylenically unsaturated monomer and 0.1 to 15 wt.-% of one or more hydrophilic ethylenically unsaturated monomer, iv) then polymerizing a second shell comprising 85 to 99.9 wt.-% of one or more nonionic ethylenically unsaturated monomer and 0.1 to 15 wt.-% of one or more hydrophilic ethylenically unsaturated monomer, v) then adding at least one plasticizer monomer having a ceiling temperature below 181° C., vi) neutralizing, to a pH of not less than 7.5 or greater, the resultant particles with one or more bases, vii) then polymerizing a third shell comprising 90 to 99.9 wt.-% of one or more nonionic ethylenically unsaturated monomer and 0.1 to 10 wt.-% of one or more hydrophilic ethylenically unsaturated monomer, viii) also optionally polymerizing one or more further shells comprising one or more nonionic ethylenically unsaturated monomer and one or more hydrophilic ethylenically unsaturated monomer, wherein a weight ratio of the swell-seed (ii) to the seed polymer (i) is in a range from 10:1 to 150:1, a weight ratio of the core stage polymer to the first shell (iii) is in a range from 2:1 to 1:5, and a weight ratio of the third shell (vii) to the second shell (iv) is in a range from 1:2 to 1.10.

9. The enzyme particle according to claim 1, wherein the coating is from 5 to 20 wt.-%, of the total weight of the enzyme particle.

10. A washing or cleaning composition, comprising enzyme particles according to claim 1.

11. The washing or cleaning composition of claim 10, wherein the washing or cleaning composition comprises bleach.

12. A food or feed composition, comprising enzyme particles according to claim 1.

13. (canceled)

14. (canceled)

15. (canceled)

Description

EXAMPLES

[0254] The present invention will now be more fully described with reference to the accompanying examples. It should be understood, however, that the following description is illustrative only and should not be taken in any way as a restriction of the invention. Numerical values provided in the examples regarding the amount of ingredients in the composition or the area weight may vary slightly due to manufacturing variability.

[0255] In the following (unlimiting) examples, the enzyme granules were coated with an aqueous coating mixture in a fluidized bed. The expert skilled in the art will know how to transfer the teachings of this application to a different coating technology.

Example 1

[0256] 75 g of Pluriol E 9000 (PEG 9000, BASF) and 250 g of AQACell 6299 X (Polystyrene particles in water, 30 wt.-% solids, BASF) were blended with 125 g of cold water by continuous stirring to obtain a homogenuous dispersion. The solid content of the coating dispersion was 33.3 wt.-%. 1080 g of enzyme core granules containing 60 wt.-% of ammonium sulfate (from BASF), 30 wt. % of china clay (from Sigma-Aldrich), 4 wt.-% solids of a polyacrylate sodium salt (Sokalan Pa. 25, from BASF), 5 wt.-% of protease and 1 wt.-% of water were introduced into a laboratory fluid bed (Glatt Procell 5) equipped with a bottom spray setup. After fluidization of the enzyme core granules, 310 g of the coating solution was sprayed onto the pellets within 31 minutes. Inlet air temperature was 56° C., and product temperature was about 40° C. When spraying of the coating solution was finished, the heating of the inlet air was turned off, and the enzyme granules were cooled until the product temperature was about 30° C. After discharging, 1080 g of enzyme granules were obtained.

[0257] The coating level of the final enzyme granule was 9.2 wt.-%. Residual moisture was 1.5 wt.-%. The total level of active enzyme was 4.5 wt.-%.

Reference Example 2

[0258] 75 g of Pluriol E 9000 (PEG 9000, BASF) and 75 g of TiO.sub.2 (TiO.sub.2, Sachtleben) were blended with 300 g of cold water by continuous stirring to obtain a homogenous dispersion. The solid content of the coating dispersion was 33.3 wt.-%.

[0259] 1030 g of the same enzyme core granules as in experiment Ex. 1 were introduced into a laboratory fluid bed (Glatt Procell 5) equipped with a bottom spray setup. After fluidization of the enzyme core granules, 310 g of the coating solution was sprayed onto the enzyme core granules within 26 minutes. Inlet air temperature was 54° C., and product temperature was about 40° C. When spraying of the coating solution was finished, the heating of the inlet air was turned off, and the enzyme granules were cooled until the product temperature was about 30° C. The product was discharged and 1040 g of enzyme granules were obtained.

[0260] The coating level of the final enzyme granule was 9.1 wt.-%. Residual moisture was 1.2 wt.-%. The total level of active enzyme was 4.5 wt.-%.

Reference Example 3-4

[0261] Using the same enzyme core granules and the same coating procedure as outlined in examples Ex. 1 and Ref. 2, further enzyme granules Ref. 3 and 4 were being produced.

[0262] Coating materials were the same like in experiments Ex. 1 and Ref. 2-4. Further binder materials were PEG 12000 (from BASF) and PVA (Mowiol 3-85, from Kuraray, which is a partially saponified polyvinylalcohol).

[0263] In all experiments, 10 parts of solids of the coating composition were sprayed on 100 parts of enzyme core granules. The final coating level in the coated enzyme particles was about 9 wt.-%.

[0264] Table 1 gives a summary of the coating compositions, based on wt.-% solids, of Ex. 1, Ref. 2-4.

TABLE-US-00001 Sample No. Ex. 1 Ref. 2 Ref. 3 Ref. 4 TiO.sub.2 50 50 50 Polystyrene particles 50 PEG 9000 50 50 25 PEG 12000 50 PVA (Mowiol 3-85, from Kuraray) 25

[0265] The coated enzyme granules of the examples have a d50 value of about 520 μm, as measured by Camsizer, wherein the measurement is based on dynamic image analysis.

(Reference) Example 5-11

[0266] For these coating experiments, enzyme cores containing 54 wt.-% of ammonium sulfate (from BASF), 30 wt.-% of china clay (from Sigma-Aldrich), 4 wt.-% solids of a polyacrylate sodium salt (Sokalan Pa. 25, from BASF), 5 wt.-% of cellulosic fibres (Arbocel FD600/30), 5 wt.-% of protease and about 2 wt.-% of water were used.

[0267] Coating materials were the same like in experiments Ex. 1 and Ref. 2-4. Further white pigments were zeolithe ZP-4A (from Silkem), talkum TP-1 (from Scheruhn) and Pergopak M (polymethyl urea resin, from Martinswerk). The coating was applied in the same procedure as outlined in examples Ex. 1 and Ref. 2.

[0268] The final coating level in the coated enzyme particles was about 9 wt.-%.

[0269] Table 2 gives a summary of the coating compositions, based on wt.-% solids, of Ex. 5-8, Ref. 9-11.

TABLE-US-00002 Sample No. Ex. Ex. Ex. Ex. Ref. Ref. Ref. 5 6 7 8 9 10 11 TiO.sub.2 25 50 Zeolithe 25 50 Talkum 75 Polystyrene particles 67 Pergopak M 25 75 25 PEG 9000 33 50 25 50 50 50 25

(Reference) Example 12-20

[0270] For these coating experiments, enzyme cores containing 31 wt.-% of ammonium sulfate (from BASF), 59 wt.-% of china clay (from Sigma-Aldrich), 4 wt.-% solids of a polyacrylate sodium salt (Sokalan Pa. 25, from BASF), 5 wt.-% of protease and about 1 wt.-% of water were used.

[0271] Coating materials were the same like in (reference) experiments 1-11. A further binder material was Luvitec VA64 (a vinylpyrrolidone-vinylacetate copolymer, from BASF). The coating was applied in the same procedure as outlined in examples Ex. 1 and Ref. 2. The final coating level in the coated enzyme particles was about 9 wt.-%.

[0272] Table 3 gives a summary of the coating compositions, based on wt.-% solids, of Ex. 12-15, Ref. 16-20.

TABLE-US-00003 Sample No. Ex. Ex. Ex. Ex. Ref. Ref. Ref. Ref. Ref. 12 13 14 15 16 17 18 19 20 TiO.sub.2 50 67 67 50 67 Zeolithe 25 Polystyrene 67 67 50 particles Pergopak M 25 PEG 9000 16.5 50 25 50 25 33 PVA 33 16.5 25 33 25 Luvitec VA64 33 (BASF)

(Reference) Example 21-22

[0273] The enzyme cores contained 59 wt.-% of magnesium sulfate (from BASF), 34 wt.-% of china clay (from Sigma-Aldrich), 1 wt.-% solids of a polyacrylate sodium salt (Sokalan Pa. 25, from BASF), 5 wt.-% of protease and about 1 wt.-% of water.

[0274] Coating materials and final coating level on the enzyme cores was the same as outlined in the previous examples. The solid content of the coating slurry was set to 15 wt.-% in both trials.

[0275] Table 4 gives a summary of the coating compositions, based on wt.-% solids, of Ex. 21, Ref. 22.

TABLE-US-00004 Sample No. Ex. 21 Ref. 22 TiO.sub.2 50 Polystyrene particles 67 PEG 9000 25 PVA 33 25

Testing of Enzyme Granules:

[0276] 1. Whiteness Assessment The whiteness assessment of the enzyme granules was carried out with a spectrophotometric instrument (Konica Minolta CM-2600d) which was calibrated before each measurement using a whiteness standard material. The sample was transferred into a cylindrical sample holder, and the cylinder was closed with a glass lid.

[0277] Three individual measurements were carried out at different locations of the enzyme granule sample, and the colorimetric CIE L*a*b values were then calculated. The L-value was a measure for the whiteness of the enzyme granules: the higher the L-value the whiter the enzyme granule.

2. Abrasion Stability

[0278] Abrasion stability of the enzyme granules was determined with a Heubach Dustmeter Type Ill. In this configuration, the enzyme granules were subjected to the action of four moving steel balls in a cylindrical container. This mechanical action generates dust, which was separated from the enzyme granules by a constant air flow through the sample container, was then collected in a microfilter.

[0279] Enzyme granule samples were sieved to 500-1250 μm prior to testing, and the bulk density was determined according to DIN/EN ISO 60. 25 ml of enzyme granules were used in the Heubach test. Measurement settings were 45 rpm rotor speed, air flow 20 L/min and 20 minutes test duration. The total amount of dust was obtained by weighting the filter before and after the test. The enzyme level contained in the dust was determined by a standard protease enzyme assay. The result of the Heubach test was the total mass of enzyme in the dust, normalized to the weight of the enzyme granule sample. Lower values mean a lower risk in enzyme dust generation during handling of the enzyme granules.

Results:

[0280] Table 5 depicts the test results from samples Ex. 1, Ref. 2-4.

TABLE-US-00005 Sample No. Ex. 1 Ref. 2 Ref. 3 Ref. 4 TiO.sub.2 50 50 50 Polystyrene particles 50 PEG 9000 50 50 25 PEG 12000 50 PVA (Mowiol 3-85, from Ku- 25 raray) L-value, CIE L*a*b 82.5 81.4 80.9 80.4 Heubach: μg protease dust/g 0.37 0.74 0.85 0.81

[0281] Polystyrene as organic white pigment in the coating has an advantage over TiO.sub.2 in whiteness and abrasion stability of the enzyme granules.

[0282] Table 6 depicts the test results from samples Ex. 5-8, Ref. 9-11.

TABLE-US-00006 Sample No. Ex. Ex. Ex. Ex. Ref. Ref. Ref. 5 6 7 8 9 10 11 TiO.sub.2 25 50 Zeolithe 25 50 Talkum 75 Polystyrene particles 67 Pergopak M 25 75 25 PEG 9000 33 50 25 50 50 50 25 L-value, CIE L*a*b 79.1 71.4 76.4 72.4 76.1 71.5 68.8

[0283] Except of TiO.sub.2, the use of inorganic white pigments in the coating yields low L-values even at high pigment level in the coating. With Pergopak Mas organic white pigment, the TiO.sub.2 benchmark is matched.

[0284] Table 7 depicts the test results from samples Ex. 12-15, Ref. 16-20.

TABLE-US-00007 Sample No. Ex. Ex. Ex. Ex. Ref. Ref. Ref. Ref. Ref. 12 13 14 15 16 17 18 19 20 TiO.sub.2 50 67 67 50 67 Zeolithe 25 Polystyrene 67 67 50 particles Pergopak M 25 PEG 9000 16.5 50 25 50 25 33 PVA 33 16.5 25 33 25 Luvitec VA64 33 (BASF) L-value, CIE 78.7 79.5 73.1 76.2 77.0 77.4 76.7 75.6 75.8 L*a*b Heubach: μg 0.18 0.07 0.46 0.124 0.43 >30 >30 0.66 protease dust/g

[0285] Whiteness and abrasion resistance of enzyme granules containing polystyrene particles as the pigment in the coating outperforms TiO.sub.2 at the same pigment level in the coating.

[0286] Table 8 depicts the test results from samples Ex. 21 and Ref. 22.

TABLE-US-00008 Sample No. Ex. 21 Ref. 22 TiO.sub.2 50 Polystyrene particles 67 PEG 9000 25 PVA 33 25 Heubach: μg protease 0.035 0.057 dust/g

[0287] The coating comprising the organic white pigment is less sensitive to abrasion than the coating comprising TiO.sub.2.