JPS62269686A - Enzyme granule and production thereof - Google Patents

Abstract

PURPOSE:An enzyme granule which is suitable for blending especially with detergents, suppresses deactivation of enzyme caused by contact in preservation and has improved shelf stability, obtained by forming a great number of fibrous protrusions on the surface. CONSTITUTION:Powder or aqueous solution of an enzyme which is derived from a bacteria and has activity in an alkali range of an aqueous solution of detergent, one more fibers of nylon, polyethylene, polypropylene, vinylon, polyester, glass, quartz, asbestos, carbon, etc., having 0.3-1.0 denier thickness and 500-1,000mum length and, if necessary, an extender, a stabilizer, etc., and other components are fed to a granulator kept at 10-50 deg.C and sprayed with water or an aqueous solution of a binder and/or a waxy substance while stirring to produce an enzyme granule having protruded fibers on the surface. The fibrous protrusions can be produced after granulation, in coating after the granu lation or in any stage after that besides in the granulation.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an enzyme granule with excellent storage stability and its 'JMTi method. More specifically, the present invention particularly relates to enzyme granules for detergents, which have fibrous protrusions on the surface and inhibit deactivation of enzymes due to contact during storage, and a method for producing the same.

[Prior Art] In recent years, enzyme-containing detergents that incorporate the action of enzymes have been in the spotlight, but typical detergent bases include, for example, anionic surfactants as the detergent main ingredient, and sodium sulfate, sulfate, etc. as builders.
Contains carboxymethylcellulose and is used as an enzyme-containing detergent.

Proteolytic enzymes (proteases) are used as detergent enzymes.
is the most commonly used, but lipolytic enzymes (lipases) and starch-degrading enzymes (amylases) are also used.

[Problems to be solved by the invention] Anionic surfactants, which are the main ingredients of detergents, lead to partial deactivation of enzymes, and furthermore, detergent bases have a fairly high alkalinity of pH 10 to 11, making it difficult to stabilize enzymes. However, in practice, it is desired to minimize the decrease in activity during storage.

[Means for solving the problem] The present inventors searched for a granulation method that suppresses the deactivation of enzymes added to various detergents, and made fibers protrude from the surface of enzyme particles to combine enzyme particles and detergents. We found that the storage stability of the enzyme was improved by preventing contact with the enzyme.

That is, as shown in Fig. 2, the enzyme granules 2 produced by the conventional method are in direct contact with the detergent components 3 in detergents, so when the detergent absorbs moisture, the activity is affected by the detergent components. We believe that it is effective to avoid contact with detergent components in order to prevent deactivation and deactivation, and as a countermeasure to this, we have added a large number of fibrous protrusions 4 on the surface of the enzyme particles, as shown in Figure 1. The present invention was completed by forming.

It has been previously proposed to add fiber components to enzyme granules for the purpose of preventing dust generation or improving strength and disintegration, and some results have been obtained (1).
No. 58-26315, Japanese Patent Application No. 59-213669), no examples have been known of stabilizing enzymes by protruding fibers to the surface of granules.

Enzyme granules have conventionally been made by appropriately blending an enzyme or an enzyme aqueous solution, a fiber component as a reinforcing material (cellulose, etc.), a thickening agent or a filler, etc., and granulating it using a granulator, and adding a protective layer if desired. However, in the present invention, fibrous protrusions in enzyme granules are produced during granulation, after granulation, during coating after granulation, or after coating during the manufacturing process of enzyme granules. It can also be formed in stages.

Prior to explaining the manufacturing method, the ingredients of the enzyme granules of the present invention will be described.

(1) Enzymes are enzymes of animal, plant, or microbial origin that are generally used in detergents. Specific examples include the following enzymes used alone or as a mixture.

Protease: pepsin, trypsin, chymo1-lipsin, cathepsin, subtilcin, collagenase, keratinase, elastase, papain, promelin, pancreatin,
Carboxypeptidase, aminopeptidase, dipeptidylpeptidase, dipeptidyl aminopeptidase; Esterase: Lipase (gastric lipase, pancreatic lipase, plant lipase, phospholipase), cholinesterase, phosphatase; Carboxylase: amylase, maltase, saccharase, cellulase ,
Lysotium, pectinase, glucosytase; Nuclease: ribonuclease, deoxyribonuclease.

Of these, alkaline proteases, alkaline esterases, and alkaline carboxylase nucleases with alkaline earth metal activity in detergent aqueous solutions are preferably used.

Enzymes are used dry or in solution.

(2) The fiber component may be one that has conventionally been used for the purpose of reinforcement, but the fibers used to form the surface protrusions in the present invention are stronger than conventional ones and are not embedded during granulation. Hard, thickness 0.3~1.0 denier, length 500~i
, oooμm is good.

The material of the fibers can be nylon, polyethylene, polypropylene, vinylon, polyester, glass, quartz, asbestos, carbon, etc. The purpose of the fiber is to isolate the granules, so it is sufficient if this can be achieved. However, it may be curly or feathery.

Bulking agents or fillers are diluents added to keep the specific activity of enzyme granules constant, and specific examples include the following.

Sulfates: 5A9 thorium, potassium sulfate, calcium sulfate,!
Magnesium acid, zinc sulfate, ferrous sulfate, sodium thiosulfate, aluminum sulfate; hydrochloride, bromide: sodium chloride, potassium chloride, calcium chloride, magnesium chloride, potassium bromide: carbonate: sodium carbonate, sodium bicarbonate, carbonic acid potassium,
Calcium carbonate, magnesium carbonate; sodium phosphate diphosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate,
Potassium dihydrogen phosphate, sodium pyrophosphate; Silicates: sodium silicate, sodium metasilicate, potassium silicate, calcium silicate; boric acid (salt) diborax, potassium borate, boric acid.

These extenders or fillers have a particle size of 100 μm or less, preferably 20 μm or less, and are used alone or in combination of two or more.

(3) Other ingredients in the enzyme granules include binders, i.e., hydrophilic substances with adhesive properties, such as polyvinyl pyrrolidone (PVP), polyvinyl alcohol, and cellulose derivatives, such as hydroxypropyl cellulose, methyl cellulose, and ruboxymethyl cellulose. Waxy substances having a melting point of 30 to 70°C, such as polyethylene glycol (PEG), ethoxylated aliphatic alcohol, polyethylene glycol monooleate, and coconut oil fatty acid monoethanolamide, are preferably used as granulating agents.

Furthermore, any coloring agent, stabilizer, reinforcing agent, etc. known in the field of granulation or enzyme preparations can be used.

Furthermore, as a coating material to enhance the shelf life of the enzyme granules, the same waxy substance as in the case of the granulating agent described above may be used as necessary, and a mixed coloring agent of titanium oxide and/or silicon oxide may be used as desired. It is attached by scattering.

In addition, adhesives for fibers include polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, dextrin, dextran, gum arabic, polyacrylamide, acrylic acid or maleic anhydride polymers, polyethylene glycol, etc. used.

[Manufacturing method] In the present invention, enzyme granules are granulated in the same manner as in the conventional method.
In a granulator maintained at 50°C, the aforementioned enzymes (powder or aqueous solution 1-35% by weight) and fibers (2-30% by weight)
This is carried out by spraying water as a liquid binder, an aqueous binder solution, and/or a waxy substance while adding other components (remaining amounts) such as fillers, stabilizers, etc. and stirring.

Fibrous protrusions on the surface of the enzyme granules can be formed during or after granulation by the following method.

1) Similar to the conventional method, enzymes, fibers, bulking agents, etc. are added at the same time, and a binder is added for granulation. This method uses fibers that are stronger than the conventional method, and uses short fibers that are not embedded in the granulation. 2) A method in which granulation is performed in advance by a conventional method, and upon completion of granulation or after sieving, before coating, fibers and adhesive are added and stirred to adhere. 3) A method in which a coating agent, fibers, and adhesive are added during coating, and the mixture is stirred to adhere. 4) A method in which fibers and an adhesive are added after coating, and the fibers and adhesive are similarly applied to the particle surface.

Any of these methods can cause the fibers to be attached to the surface in a protruding manner. When the fibers are attached after granulation, it is not necessarily necessary to add fibers to the initial particles, but from the viewpoint of strength, it is preferable to granulate the fibers with the fibers added in advance.

In addition, when using the above-mentioned adhesive, it is generally sprayed in the form of an aqueous adhesive solution in which fibers are dispersed and mixed, but the concentration is 5.
~20% is appropriate.

[Example] Hereinafter, the effects of the present invention will be specifically explained with reference to Examples and Comparative Examples.

Comparative Example As a granulating composition, a composition consisting of 180 g of enzyme powder, vinylon fiber 809, and 1,740 g of finely powdered sodium sulfate was granulated using a L)IA-10 type granulator manufactured by Nara Kikai. Granulation is carried out at room temperature. Enzymes, fibers, and sodium sulfate are first charged into a granulator, and the main shaft is set at 35 rpm.
After mixing for 5 minutes by rotating at 3.00 rpm, continue to rotate and mix at 22 rpm with a two-fluid spray.
0 g of water was added over 7 minutes and granulation was carried out for 10 minutes to obtain granules without protruding fibers. The proteolytic enzyme subtilisin BPN was used as the enzyme.

The fiber used was 0.3# in length.

The stability of the obtained granules was measured as follows.

Place 0.25 g of granules in a container, add 5 g of detergent, mix well, and place in a constant temperature and humidity chamber at a temperature of 40'C and a relative humidity of 80%, after 40 hours, 110 hours, and 160 hours. To measure the residual activity of each sample
18), the enzyme activity residual rate was calculated from this, and Table 1
The results shown are obtained.

Example 1 As a granulation composition, a composition consisting of enzyme powder, ioog vinylon fiber 200g, and finely powdered sodium sulfate 1.6209 was placed in a granulator and granulated in the same manner as in Example 1 to form a large number of fibers on the surface. A granule with a protruding granule was obtained. The fiber is
A piece with a thickness of 0.5 denier and a length of i and omm was used.

As an enzyme, the proteolytic enzyme subtilisin BPN'
was used.

The stability of the obtained granules was measured in the same manner as in the comparative example, and the results shown in Table 1 were obtained.

Example 2 IKg of the granules obtained in Example 1 were placed in a mixer heated to 60°C, and 709 wax was added to coat the granules.

The stability of the obtained granules was measured in the same manner as in the comparative example, and the results shown in Table 1 were 17.

Example 3 1 kg of the granules obtained in Comparative Example 1 was placed in a mixer heated to 60°C, and 80 g of vinylon fiber (0.5 denier, length 1.Os) and 609 wax were added and mixed. death,
Fibers were attached to the surface of the granules. Stability of the obtained granules i
The main measurements were performed in the same manner as in the comparative example. The results are shown in Table 1.

Example 4 The granules obtained in Example 1 were coated in the same manner as in Example 3 to form fibrous protrusions on the surface. The stability of the obtained granules was measured in the same manner as in the comparative example, and the results shown in Table 1 were obtained.

Table 1 = Enzyme activity residual rate (%) Examples 5 to 10 Various enzymes and granulation components were used in the mixing ratios shown in the column of granulation conditions in Table 2, and in the same manner as in the comparative example, particles protruding from the surface were Six types of fiber-free granules were manufactured.

Next, for these granules, various adhesives and fibers were used in the mixing ratios listed in the table according to the method shown in the column of fiber adhesion conditions in Table 2, and the mixture was heated to 60'C. Granules having protruding fibers on the surface were obtained by processing in a container.

These granules were heated under 40'C, 80% R, H conditions for 1
After holding for 60 hours, the residual rate of enzyme activity was determined. The results are shown in Table 2.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing the state of the enzyme granule of the present invention in a detergent, and FIG. 2 is an explanatory diagram showing the state of a conventional enzyme granule in a detergent. Symbols in the figure: 1... Enzyme granules of the present invention; 2... Conventional enzyme granules; 3... Detergent particles; 4... Fibers. Figure 1 Figure 2

Claims (1)

[Claims] 1) An enzyme granule characterized by having a large number of fibrous protrusions formed on its surface. 2) The fibrous protrusions are nylon, polyethylene, polypropylene, vinylon, polyester, glass, quartz,
The enzyme granule according to claim 1, comprising one or more types of fibers selected from asbestos and carbon. 3) The enzyme granule according to claim 1, wherein the fibrous protrusions are linear and/or curled and/or feather-like. 4) A method for producing enzyme granules, which comprises mixing fibrous chips and granulating them with a large number of fibers protruding from the surface. 5) Production of enzyme granules characterized by adding fibrous chips and an adhesive to the granulated enzyme granules and stirring in a granulator or coating machine to adhere a large number of fibers to the surface. Method. 6) The adhesive is a waxy substance, polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivative, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, dextrin, dextran, gum albia, polyacrylamide, a polymer of acrylic acid or maleic anhydride, or a polymer of these The manufacturing method according to claim 5, which is an aqueous solution. 7) A method for producing enzyme granules, which comprises adding a coating agent, fibrous chips, and an adhesive to the enzyme granules and stirring them to form a large number of fibrous protrusions on the surface. 8) The adhesive is a waxy substance, polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivative, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, dextrin, dextran, gum arabic, polyacrylamide, a polymer of acrylic acid or maleic anhydride, or a polymer of these. The manufacturing method according to claim 7, which is an aqueous solution of.