JP2696230B2 - Enzyme granules and granulation method - Google Patents

Description

The present invention relates to industrial enzymes used in detergents, bath preparations, pharmaceuticals, fibers, leather, feed, fertilizers, and other various fields. The present invention relates to an enzyme granule which stabilizes an enzyme which is unstable to a target water, particularly for detergents and baths, and a method for granulating the enzyme granule in a non-aqueous system.

[Related Art] Various industrial enzymes, for example, enzymes for detergents, are mainly granulated to a certain particle size in detergents in order to ensure the safety of the enzymes. In order for this enzyme granule to exert a sufficient washing effect, it is necessary to ensure the storage stability, solubility, low dust generation and other product characteristics of the product.

The granulation method for producing these enzyme granules is an important point for exerting the enzyme function, and various studies have been made so far. For example, Japanese Patent Publication No. 58-26315 discloses a method using water and a wax-like substance as a binder (binder) used at the time of granulation.
Polyvinylpyrrolidone, dextrin, polyvinyl alcohol, various cellulose derivatives and the like are used. JP-A-60-262900 discloses a binder obtained by dissolving starch and its derivatives, sugar, cellulose derivative, gelatin, polyvinyl alcohol, etc. Granulation using However, when granulating using an aqueous binder, there are various problems such as that the enzyme itself is easily deactivated, that there is a large amount of adhesion to the granulator, and that the shape of the granules is poor.

In order to solve this, a method of granulating in a non-aqueous system has been proposed. Japanese Patent Publication No. 58-26315 discloses a binder such as ethoxy fatty acid alcohol (mp = 46 ° C.) or coconut oil monoethanolamide (mp = 67 ° C.), and international publication number WO.
87/04184 uses polyethylene glycol (PEG) (molecular weight 3000-8000), polyoxyethylene propylene copolymer and the like. Among them, granules using coconut oil monoethanolamine are remarkably poor in solubility in water, and therefore are unsuitable for granules for detergents and baths. In many cases, polyethylene glycol is used.

Next, as described above, in addition to storage stability, the enzyme granule is required to have properties such as good solubility, low dusting properties of the enzyme, and high whiteness. These properties must also be satisfied. Reduced dusting,
In order to improve the whiteness, the granules are generally overcoated with a polyethylene glycol-based coating and a TiO ₂ -based cosmetic.

Even with the enzyme granules obtained in this way, the storage stability when blended in a detergent depends on the type of the detergent, and some detergents are considerably inactivated. There is no fact. Therefore, it is necessary to examine the formulation of the enzyme granule depending on the type of detergent to be blended. Also, in the field of enzymes used for bath preparations, at present, most of them are blended in the form of powdered enzymes, and are considerably unstable and often inactivated, as in the case of detergent enzymes, and in many cases, as in the case of detergent enzymes. It is desired to granulate and stabilize.

[Problems to be Solved by the Invention] The absence of such versatile enzyme granules is as follows.
Surfactants, chelating agents, alkalis, contained in detergents
This is because the composition of substances that affect enzyme activity, such as builders, varies considerably depending on the type of detergent.

That is, these detergent components strongly act on the enzyme, and many components are liable to cause denaturation of the enzyme. When the enzyme comes into contact with these components in the detergent, the detergent component is significantly deactivated. Further, since the detergent is composed of a water-soluble component and has high hygroscopicity, the amount of the detergent penetrating into the granule caused by the absorbed moisture, the penetration rate, and the like considerably affect the storage stability.

Therefore, under the present circumstances, in order to stabilize each enzyme in the detergent to be blended, an enzyme formulation suitable for each detergent was performed.

Since this formulation is a rather difficult task, the present inventors have studied to develop a versatile enzyme granule applicable to all commercially available detergents while satisfying other physical properties. Most of the bath enzyme is mixed in a powder state, and is considerably unstable like the detergent enzyme. Therefore, it is necessary to stabilize this enzyme,
We studied to develop a versatile enzyme granule.

[Means for Solving the Problems] The present inventors have intensively studied to solve the above problems from the viewpoint of the binder and the coating agent used when granulating by a heating and melting method in a non-aqueous system.

The present inventors have shown that granules obtained by a heat-melting method using a PEG-based binder (International Publication No. WO87 / 04184) to improve the stability of enzymes are good. Stability was still insufficient for application. As a result of various studies on conventional granules, it was considered that the key to solving the problem was how to reduce the hygroscopicity of the granules and how much the permeation amount of detergent components could be reduced.

As a process in which the detergent component of the base penetrates into the enzyme granule when the enzyme granule is blended, first, the detergent and the granule absorb moisture, and then the polyethylene glycol, which is a surface coating agent, is dissolved and the two are mutually diffused. It is thought to diffuse and permeate into the granules.

Therefore, in order to suppress this diffusion, it is necessary to use a bander and a coating agent having a low hygroscopicity as much as possible, and to select a substance having low compatibility as an interaction between the surface coating agent and the binder as the binder and the coating agent. It is.

The present inventors have studied various substances and found that methoxypolyethylene glycol in which the terminal OH group was methoxylized is effective as a binder in order to reduce the hygroscopicity of polyethylene glycol. completed.

That is, the present invention provides: 1) a granulation method for enzyme granules, wherein methoxypolyethylene glycol is added to the bulk powder of the enzyme at least 5% by weight to 80% by weight based on the total amount of the granule components. 2) The method as described in 1 above, wherein methoxypolyethylene glycol is used as a binder or a coating agent, and is heated and melted at a temperature higher than its melting point to granulate. Enzyme granulation method characterized by adding 5% by weight or more and 40% by weight or less to the granule component and agitating and granulating. 4) Methoxy polyethylene glycol is used as the whole granule component in the raw material of the enzyme. 5% by weight of methoxypolyethylene glycol based on granulated particles, wherein spray granulation is performed by adding 40% by weight or more and 80% by weight or less. Enzyme granulation method characterized by adding over 15% by weight or less and overcoating, 6) At least 5% by weight based on the original enzyme powder and all granulated components
Enzyme granules containing at least 80% by weight of methoxypolyethylene glycol; 7) Having an overcoat layer containing 5% by weight to 15% by weight of methoxypolyethylene glycol based on the granulated particles And 8) wherein the enzyme is a detergent enzyme or a bath agent enzyme.
Or an enzyme granule according to item 7.

The methoxypolyethylene glycol that can be used in the present invention has a molecular weight of preferably from 1,000 to 8,000, particularly from 2,000 to 6,000.
A degree is optimal.

As the granulation method, any method can be used as long as it can apply a heat melting method, and for example, stirring granulation or spray granulation can be used.

In the case of agitation granulation, the granulation temperature is a temperature equal to or higher than the melting point of the binder, preferably from the melting point + 5 ° C to + 40 ° C.
Granulate at a temperature of When the melting point is close to the melting point, the viscosity of the binder is high and the granulation property is poor. Therefore, it is preferable to granulate at a temperature higher than the melting point by 5 ° C. or more. On the other hand, since the enzyme has poor temperature stability at high temperatures, it is preferable to granulate at a temperature as low as possible, and from the relationship between the two, it is optimal to granulate at a melting point of about + 5 ° C to about + 40 ° C.

The stirring granulator may be either a vertical type or a horizontal type, but in the case of the granulation method according to the present invention, a device capable of heating with hot water, steam, electricity or the like is required.

The amount of the binder to be added varies depending on the type of granulation method. For example, in the case of stirring granulation, 5% to 40% by weight is used.
In the case of spray granulation, about 40% to 80% by weight is appropriate.

In the case of spray granulation, any device capable of cooling with cold air may be used. For granulation, methoxypolyethylene glycol as a binder is melted in advance at a temperature at which the viscosity is such that it can be sprayed (1000 cp or less), and after adding and mixing the target enzyme, it is quickly sprayed and solidified by cooling. In this case, the amount of the binder is required to be about 40% by weight to 80% by weight in order to maintain fluidity to such an extent that the binder can be sprayed.

When methoxypolyethylene glycol is to be used as an overcoating agent, the one having a relatively low molecular weight of about 1,000 to 2,000 is preferable. The coating is performed at a temperature equal to or higher than the melting point as in the case of granulation, but the coating is performed at a temperature equal to or lower than the softening point of the binder of the inside particles so that the inside particles do not melt and break. For example, when particles granulated with polyethylene glycol 5000 are coated with methoxy polyethylene glycol 1500, PEG 50
It is necessary to coat with a softening point of 00 or below 53 ° C. When used as an overcoat agent, the amount of methoxypolyethylene glycol is usually 5 to 15% by weight. If the amount is less than 5% by weight, the dusting properties and whiteness are not improved, and if it is more than 15% by weight, granulation occurs again, causing large grains.

The target enzyme can be used in most cases as long as it is generally used, such as for detergents, bath agents, and fiber treatment, and is not particularly limited. Therefore, enzymes of any origin such as animals, plants, and microorganisms can be used, and the present invention can be applied to proteases, amylases, lipases, and the like used in various fields.

In the present invention, in order to keep the specific activity of the enzyme granules constant, extenders, excipients and other fillers conventionally used as diluents can all be used, but preferably reduce the hygroscopicity of the granules. For this purpose, it is preferable that the extender or the like be made of a substance having as little hygroscopicity as possible. For example, calcium sulfate and calcium carbonate are preferable as the filler.

[Effects of the Invention] The present invention provides an enzyme granule granulation method using methoxypolyethylene glycol as a binder or a coating component, and an enzyme granule. Compared with a conventional enzyme granule using polyethylene glycol, Since it has excellent storage stability when blended in a detergent or the like, there is no need to change the formulation of the granule depending on the type of the detergent or the like, and it can be used as a versatile enzyme granule.

[Examples] Hereinafter, the present invention will be described with reference to representative examples.
These are merely examples, and the present invention is not limited only by these examples.

Example 1 250 g of alkaline protease (API-21), 1300 g of calcium sulfate (1/2 water salt) as a bulking agent, titanium oxide as a whitening agent
60g and 390g of monomethoxy polyethylene glycol (molecular weight 5000) as a binder were stirred with a granulator (Fuji Sangyo VG
-10), spindle speed 250rpm, chopper 3000rpm
And heated at 70 ° C with jacket heating. After granulation is completed, the particles are discharged and a fluidized cooler (Fuji Sangyo ST
Cooled in REA-1).

As a result of sieving the obtained granules through # 14 to # 42 (1.19 to 0.35 mmφ), the particle size distribution was as follows.

# 14 or more 14% # 14 to 42 75% # 42 or less 11% The granulation yield was as good as 75%, and no adhesion to the machine wall was observed at all, and it was an excellent granulation binder.

Next, add polyethylene glycol 1500 to 1500 g of coarse granules
g, and 225 g of a cosmetic agent (titanium oxide 40% by weight, talc 50% by weight, silica 10% by weight) were added, and overcoated at 45 ° C.

The solubility, whiteness, and dusting property of this granule in a detergent solution were measured, and the following results were obtained.

I. Solubility in detergent solution: dissolution rate 95% at 3 ° C for 3 minutes. Whiteness: L * (color system recommended by CIE 1976) = 81%, equivalent to commercial products c. Dust generation (unilever-type extrusion test): 1
20PU / 60g Example 2 270 g of alkaline protease (subtilisin-Carlsberg), calcium sulfate 1/2 H ₂ O 1300 as bulking agent
g, 40 g of titanium oxide as a whitening agent, and 390 g of monomethoxypolyethylene glycol (molecular weight 5000) as a binder.
Granulation was performed under the same conditions as described above. The granulation yield was as good as 87%.

Next, add 1500 g of polyethylene glycol 1500 to 1500 g of this granule.
g, 225 g of the same cosmetic agent as in Example 1 was added, and overcoated at 46 ° C.

As for the characteristics of the granule, the solubility was 93% at 3 minutes at 10 ° C., the whiteness L * = 82%, and the dusting property was as good as 135 PU / 60 g.

Example 3 Alkaline protease (subtilisin Carlsberg) 260 g, calcium sulfate 1/2 H ₂ O 1290 as bulking agent
g, 60 g of titanium oxide as a whitening agent, and 390 g of polyethylene glycol (molecular weight 5000) as a binder were granulated under the same conditions as in Example 1 using a stirring granulator. The granulation yield was as high as 81%.

1500 g of this granule is added to 150 g
100 g of 0 and 220 g of the same cosmetic agent as in Example 1 were added and overcoated at 49 ° C.

Storage stability test The granules obtained in Examples 1, 2 and 3 were blended with various commercially available detergents (8 types, A to H), and the storage stability was measured.
The measurement conditions are as follows.

Detergent amount 50g Enzyme granule amount 0.5g Container 100ml Plastic temperature 40 ° C Humidity 80% Time 2 weeks Obtained activity after 2 weeks is shown in Table 1. Table 1
As comparative examples, two types of enzyme granules currently on the market (a, b)
The result of the storage stability was also added.

As is apparent from Table 1, the granules produced by the granulation method of the present invention are much more stable than other granules currently on the market, and can be applied to all detergents.

Example 4 1200 g of bank creatine enzyme (JP 4.0) and 2800 g of monomethoxypolyethylene glycol (molecular weight 4000) at 80 ° C.
The mixture was melt-stirred and mixed in a jacketed container with hot water, supplied to a heated 250 mmφ, 7000 rpm rotary desk in 8 minutes, and spray-cooled to obtain granules. The storage stability of the granules in a bath agent was measured. That is, after adding a humectant, a fragrance, a dye, etc. to the basic composition of the bath agent (a mixture of 50% by weight of sodium bicarbonate and 50% by weight of sodium sulfate), the raw powder or the above-mentioned coated granule is added, and And an accelerated test for 2 weeks was performed.

Two weeks later, the residual activity was measured. As a result, the bulk enzyme had almost no activity, but the coated granules of the present invention showed 73%
It remained.

Therefore, the stability of the granules of the present invention to bath agents was much more stable than granules without overcoating.

Claims (8)

(57) [Claims] (1) methoxypolyethylene glycol is added in an amount of at least 5% by weight based on the total amount of granules to the enzyme powder.
A method for granulating an enzyme granule, wherein the granulation is performed by adding less than 10% by weight. 2. The method according to claim 1, wherein methoxypolyethylene glycol is used as a binder or a coating agent, and the mixture is heated and melted at a temperature not lower than its melting point to perform granulation. 3. A method for granulating an enzyme, wherein methoxypolyethylene glycol is added to the raw powder of the enzyme in an amount of 5% by weight or more and 40% by weight or less based on all granules, followed by stirring and granulating. 4. A method for granulating an enzyme, wherein methoxypolyethylene glycol is added to the raw powder of the enzyme in an amount of from 40% by weight to 80% by weight based on the total amount of the granules, followed by spray granulation. 5. A method for granulating an enzyme granule, wherein methoxypolyethylene glycol is added in an amount of 5% by weight or more and 15% by weight or less based on the granulated particles to perform overcoating. 6. An enzyme granule comprising at least 5% by weight to 80% by weight of methoxypolyethylene glycol based on the raw enzyme powder and all granulated components. 7. An enzyme granule having an overcoat layer containing 5% by weight to 15% by weight of methoxypolyethylene glycol based on the granulated particles. 8. The enzyme granule according to claim 6, wherein the enzyme is a detergent enzyme or a bath enzyme.