JPH0482040B2 - - Google Patents

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides enzyme granules for detergents, which have less enzyme deactivation during production and have a narrow particle size distribution, making it easy to control the particle size. Regarding the manufacturing method.

[Conventional technology and its problems]

Powder detergents for clothing often contain various enzymes to enhance their cleaning action. Although these enzymes are expected to perform their original enzymatic action during the washing process, they are likely to be deactivated by detergent components during storage, and countermeasures have been taken to prevent this. That is, the basic method is to make the contact area with the detergent as small as possible by granulating the enzyme, and at the same time, a stabilizer has been used in combination.

On the other hand, granulation of enzymes is also meaningful for the purpose of avoiding contact with enzymes by workers and consumers as much as possible during the production or use of detergents.

Therefore, for both reasons, there has been a need for enzyme granules that are hard to break and do not generate dust.

To achieve this objective, a method is known in which the enzyme is dispersed in a substance such as molten polyethylene glycol or a nonionic surfactant, and then spray cooled to obtain spherical granules. However, when dispersed in a substance with a high melting point, the enzyme is deactivated by heat due to the long time required for spray cooling, and in a substance with a low melting point, problems such as sticky granule surfaces occur.

Separately, fibers are mixed to make granules,
Methods of rendering particles unbreakable when subjected to mechanical forces are also known in the art. In this case, if the kneaded material containing fibers is extruded and granulated, for example, the productivity will drop significantly.

In addition, when attempting to obtain strong particles by wet granulation using an aqueous solution of starch, carboxymethyl cellulose (CMC), etc. as a binder, the particles are exposed to high temperatures during the drying process, causing enzyme deactivation. Probability is high.

Therefore, in the enzyme granulation process, it has been desired to develop a technology that allows particle size to be controlled arbitrarily to some extent, has a narrow particle size distribution, and shortens the heating time as much as possible. This is expected to not only reduce the burden on equipment for the classification and recovery process of the granulated product, but also eliminate the deactivation of enzymes when re-granulating the recovered product.

[Means for solving problems]

As a result of intensive research to solve the above problems, the present inventors discovered a method for producing enzyme granules with almost no enzyme deactivation during the granulation process and a narrow particle size distribution, and completed the present invention. .

That is, the present invention provides a detergent enzyme powder containing a core substance consisting of water-soluble particles with an average particle size in the range of 0.2 mm to 1.2 mm and a water-soluble organic material with a melting point or softening point of 35°C to 70°C. After heating the water-soluble organic binder together with the binder while stirring with a stirring rotary granulator to a temperature above the melting point or softening point, and then cooling, the average particle size of the granules is 1 times the average particle size of the core material. The present invention provides a method for producing enzyme granules for detergents, which is characterized by dry granulation so that the granules are doubled in size.

The production method of the present invention is characterized in that an enzyme is attached to the surface of core particles using a binder to form spherical particles. Moreover, at this time, it is important not to cause aggregation of the core particles. The granules obtained in this way have a spherical shape with a single core particle at the center and the enzyme fixed on the surface with a binder. Spherical granules with a narrow particle size distribution are obtained when compared to conventional products. Moreover, the particle size of the granules can be determined by selecting the particle size of the core particles.
It has the advantage of being easily controllable.

The components used in the present invention and the granulation method will be explained below.

Enzyme The enzyme used in the present invention performs its original enzymatic action during the washing process, and examples include one type or a mixture selected from protease, esterase, and carbohydrase.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, splicitin, papain, aminopeptidase, carboxypeptidase, and the like.

Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, phosphotases, and the like.

Examples of carbohydrases include cellulase, maltase, satucarase, amylase, pectinase, α- and β-glycosidases, and the like.

For detergents, enzymes produced by microorganisms obtained by culture are advantageous in terms of cost. In the present invention, a dried powder after culturing and separation is used. Its average particle size is 20% of the average particle size of nuclear material.
The following are desirable. During powdering, enzyme stabilizers such as calcium chloride and powdering aids such as Glauber's salt and sodium chloride may be added.

Granulation core material The granulation core material is selected from those that meet the following requirements.

(1) It must be water-soluble; in other words, since the product of the present invention is an enzyme granule for detergent formulation, it must be soluble in water.

(2) Does not inhibit enzyme activity or impair enzyme stability.

(3) Items with an average particle diameter of 0.2 mm to 1.2 mm. In principle, the particle diameter referred to here refers to the value of primary particles, but this does not apply to particles that have been granulated in advance and can be virtually regarded as primary particles. In the present invention, a core material having an average particle size of about 50% to 100% of the average particle size of the desired final granules is used. The narrower the particle size distribution is, the more desirable it is, and in particular, excluding coarse particles with a size twice or more the average particle size brings about good results.

(4) In addition, it must have a melting point or softening point of 80 degrees or higher, low hygroscopicity, high mechanical strength, and low stickiness.

The substances that meet the above requirements differ depending on the type of enzyme used, but specific examples of nuclear substances that can be generally used include sodium chloride, potassium chloride, Glauber's salt, soda carbonate, and sugar. can.

Binder One of the features of the present invention is dry granulation using stirring and rolling, as described later in the granulation method.
Therefore, the binder is selected from water-soluble organic substances having a melting point or softening point of 35°C to 70°C.
Specific examples include nonionic surfactants such as polyethylene glycol, polyoxyethylene-polyoxypropylene glycol, and polyoxyethylene alkyl ether.
One or a mixture of them can be used. If it is liquid at room temperature and has a melting point or softening point of less than 35°C, the granulated product tends to cause caking during storage, which is not preferable. Moreover, if the temperature exceeds 70°C, the melting temperature during granulation will be too high and the enzyme may be deactivated, making it unsuitable.

Other components In the present invention, in addition to the enzyme and binder,
Mainly to improve the whiteness of the granules, the average particle size is
Titanium oxide, talc, silica, clay, etc. with a diameter of 10 μm or less can be used. In order to stabilize the enzyme, it is also possible to use inorganic salts such as various calcium salts and magnesium salts, or organic substances such as surfactants, sugars, and carboxymethyl cellulose. Furthermore, synthetic hectorite or sepiolite can be blended to adsorb odorous components derived from culture. In addition, by blending pigments and dyes,
It is also optional to color the enzyme granules.

These components may be added in advance during the enzyme powder manufacturing process or may be added during the granulation process of the present invention.

The blending ratio of detergent enzyme, nuclear material, and water-soluble organic binder is 9 parts enzyme powder to 100 parts by weight of nuclear material.
-100 parts by weight of the water-soluble organic binder and 9-60 parts by weight of the water-soluble organic binder, and the weight ratio of the enzyme powder to the water-soluble organic binder is preferably in the range of 1 part of the enzyme powder to 0.2 to 2 parts of the water-soluble organic binder.

Granulation method The present invention is characterized by dry granulation using a stirring and rolling granulator. Specific examples of stirring rotary granulators include Henschel mixer (Mitsui Miike Kakoki Co., Ltd.), high-speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator (Fuji Sangyo Co., Ltd.), etc. be able to. What these types have in common is that they have a vertical stirring shaft with stirring blades attached inside the vertical mixing tank. A horizontal granulator with a horizontal stirring shaft, the Lödeige Mixer (Lödeige GmbH, West Germany), can likewise be used.

In this tank, core particles, binder, enzyme powder,
Other ingredients are added as necessary, and the mixture is gently stirred and mixed while flowing a heating medium such as hot water through the jacket of the granulator. Care must be taken because vigorous mixing at this point will cause destruction of the core particles. Eventually, when the temperature of the raw material in the tank exceeds the melting point or softening point of the binder, granulation begins centered on the core particles, but spherical particles are formed by the rolling action on the surface of the stirring blade. . If the stirring is continued further, coarse clumps may be formed due to agglomeration of particles, and the thermal effect on the enzyme will also increase, which is undesirable. However, it is generally difficult to detect the optimal end point of granulation. Taking advantage of the fact that the power required for stirring (e.g. electric current value) increases when granulation begins, it is easy to determine the composition of the desired granulate and to test it in advance with the stirring rotary granulator to be used. can be done. Then, it is cooled to obtain the desired enzyme granules for detergent.

The enzyme granules obtained by the production method according to the present invention can be coated with polyethylene glycol or a nonionic surfactant, if necessary. Moreover, at this time, there is no problem in using together the materials mentioned in the section of the other components above.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail by describing examples of the present invention, but the present invention is not limited to these examples.

In addition, in the following examples, all percentages are weight percentages.

Example 1 <Raw materials> Enzyme powder Calcium chloride and Glauber's salt were added to an aqueous solution of alkaline cellulase cultured and collected from a bacterium belonging to the genus Bacillus whose microbial deposit number is FIKE No. 1138. A powder with an average particle size of 50 μm obtained by drying with a type spray dryer was used. The amount of calcium chloride and Glauber's salt is 0.5% each based on the dry product.
It is 48%.

Nuclear material The average particle size is 610 μm, with 11 particles smaller than 500 μm.
%, particles of 700 μm or more were 9% sodium chloride.

Binder Polyethylene glycol 6000P (NOF Corporation)
was used.

<Composition> Enzyme powder 35%, nuclear material 45%, binder 15%,
Titanium oxide 5%.

<Pelletization operation> High speed mixer (Fukae Kogyo Co., Ltd., FS-10)
All of the above raw materials (total 6 kg) were put into a mold) and mixed and stirred at a stirring blade tip speed of 5 m/sec while 85°C hot water was flowing through the jacket. The temperature of the contents is 65
When the temperature rose to 30°C, the mixer was discharged, immediately transferred to a fluidized bed, and cooled to 30°C.

<Physical properties of granulated product> The average particle diameter of the obtained enzyme granules was 810 μm.
3.6% had a particle size of 1410 μm or more, and 1.8% had a particle size of 350 μm or less. This shows that the present invention can easily produce granules with a very narrow particle size distribution.

The enzyme activity of the raw enzyme powder and the granulated product was measured by the dinitrosalicylic acid method, and the activity retention rate during the granulation process was determined to be 100%, that is, there was no inactivation at all.

Example 2 <Raw materials> and <Blend> are the same as in Example 1.

<Pelletization operation> Henschel mixer (Mitsui Miike Kakoki Co., Ltd., FM
-208 type), put all the above raw materials (total 8 kg),
While flowing hot water at 85°C through the jacket, mixing and stirring were carried out at a stirring blade tip speed of 13 m/sec. When the temperature of the contents rose to 67°C, the mixer was discharged and immediately transferred to a fluidized bed to cool to 30°C.

<Physical properties of granulated product> The average particle diameter of the obtained enzyme granules was 750 μm.
2.0% had a particle size of 1410 μm or more, and 3.4% had a particle size of 360 μm or less. This example also shows that the present invention produces less fine powder and coarse particles.

In this example as well, the activity retention rate during the granulation process was found to be 100%, confirming that the conditions for the enzyme were satisfactory.

Example 3 <Raw materials> The same enzyme powder and binder as in Example 1 were used.

Nuclear material The average particle size is 250 μm, with 23 particles of 125 μm or less
%, and 8% of particles of 350 μm or more were used.

<Composition> Enzyme powder 35%, nuclear material 42%, binder 18%,
Titanium oxide 5%.

<Pelletization operation> Granulation was carried out using the same equipment and conditions as in Example 1, and the enzyme granules were obtained by cooling.

<Physical properties of granulated product> The average particle diameter of the obtained enzyme granules was 340 μm.
7.4% had a particle size of 710 μm or more, and 0.9% had a particle size of 177 μm or less.

This example also shows that according to the present invention, granules having a very narrow particle size distribution can be easily obtained.

When the activity retention rate in the granulation process was determined, it was 100% in this example as well.

Comparative Example 1 <Raw Materials> The same enzyme powder as in Example 1 was used, and the binder was polyethylene glycol #4000 (NOF).
Co., Ltd.) was used.

<Composition> Enzyme powder 30%, binder 65%, titanium oxide 5
%.

<Pelletization operation> Melt and mix a total of 20 kg of raw materials at 85℃,
Spray cooling was performed from a pressure nozzle with a diameter of 1.6 mm at a pressure of 50 kg/cm ² to obtain spherical enzyme granules. This is the first sample.

Fine powder of 125μm or less obtained by classifying these granules
2.5Kg was melted again and spray cooled in the same manner as the first time. This is the second sample.

<Physical properties of granulated product> The average particle diameter of the first sample was 220 μm.
0.3% had a particle size of 500 μm or more, and 14.7% had a particle size of 125 μm or less.

In the above example, the fraction of particles with a particle diameter of about one-half or less of the average particle diameter of the granules was 5% or less, whereas in this comparative example, this amount was as high as 14.7%, and the particles It is clear that the diameter distribution is wide and the burden on the equipment for classification and collection operations will inevitably be greater than in the present invention.

When the activity retention rate in the granulation process was determined, the first sample was 96% and the second sample was 89%, which is clearly inferior to the present invention in this aspect as well.

Comparative Example 2 <Raw Materials> The same enzyme powder as in Example 1 was used, and the binder was carboxymethyl cellulose with a degree of etherification of 0.7 and a purity of 95%. In addition, mirabilite was used.

<Composition> Enzyme powder 35%, binder 0.5%, titanium oxide 5%, mirabilite 59.5%.

<Pelletization operation> The raw materials except the binder are mixed, and a 4% aqueous solution of the binder is added and mixed. The total weight is 3Kg. This is extruded using a granulator (Fuji Paudal Co., Ltd.).
EXD CS−100) was granulated into a columnar shape with a diameter of 0.9 mm.
In addition, Marmerizer (Fuji Paudal Co., Ltd., QJ-
400) and then dried in a fluidized bed with hot air at 85°C until the moisture content was 3% or less.

<Physical properties of granulated product> The average particle diameter of the obtained enzyme granules was 920 μm.
0.8% had a particle size of 1410 μm or more, and 2.7% had a particle size of 500 μm or less. In this example, granules with a very narrow particle size distribution equivalent to or better than that of the present invention can be obtained.

However, when the activity retention rate during the granulation process was determined, it was 97%. This is thought to be caused by the heat during drying.

Claims (1)

[Scope of Claims] 1 Detergent enzyme powder is made of a core substance consisting of water-soluble particles with an average particle diameter in the range of 0.2 mm to 1.2 mm and a water-soluble particle with a melting point or softening point of 35°C to 70°C. The water-soluble organic binder is heated together with the organic binder while being stirred by a stirring rotary granulator to a temperature higher than the melting point or softening point of the water-soluble organic binder, and then cooled until the average particle size of the granules is 1/2 of the average particle size of the core material. double to 2
A method for producing enzyme granules for detergents, which is characterized by dry granulation to double the size. 2. The manufacturing method according to claim 1, wherein the detergent enzyme is one or a mixture selected from protease, esterase, and carbohydrase. 3 The nuclear material is sodium chloride, potassium chloride,
The manufacturing method according to claim 1 or 2, wherein the salt is one selected from Glauber's salt, soda carbonate, and sugar or a mixture thereof. 4 The organic binder is polyethylene glycol,
The manufacturing method according to any one of claims 1 to 3, wherein the method is one selected from nonionic surfactants or a mixture thereof.