JP2008161189A - Method for producing enzyme-containing granule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an enzyme-containing granule having high activity without causing deactivation of an enzyme when the enzyme is granulated into a granular state. <P>SOLUTION: The method for producing an enzyme-containing granule has a process (A) for drying an enzyme-containing solution to give a powdery enzyme preparation and a process (B) for dry-granulating the powdery enzyme preparation obtained by the process (A). The process (A) and/or the process (B) is carried out in the presence of one or more kinds selected from among an amino acid and its salts. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an enzyme-containing granulated product, and particularly to a method for producing an enzyme-containing granulated product for detergent.

  In many cases, various detergents and bleaching agents for clothing are blended with various enzymes in order to further increase the detergency. This enzyme dissolves in water at the time of washing when the detergent is used and exhibits its effect. Therefore, in the period from the production of the powder detergent to the use, it is necessary to keep the function of the enzyme in the powder detergent without being deactivated as much as possible. For this purpose, the contact between the enzyme component and the detergent component or outside air must be minimized. In addition, from the viewpoint of safety, it is necessary that workers during manufacture and consumers during use avoid contact with enzymes as much as possible. Therefore, the enzyme is usually blended as a granulated product when blended with a powder detergent.

Since these enzymes are deactivated over time due to the presence of water, various methods for improvement have been developed. For example, in order to stabilize an aqueous enzyme solution, a method of adding gelatin, polyhydric alcohol and ethyl alcohol (Patent Document 1), mixing an amino acid with an alkaline protease, and stabilizing the enzyme in a detergent base material or in an alkaline solution There is a technique (Patent Document 2) and the like. At present, in order to develop sufficient activity during washing without deactivation during storage, the detergent enzyme powder is heated together with a water-soluble core substance and a water-soluble organic binder while stirring with a stirring tumbling granulator. A method of cooling and dry granulation to form granules is the mainstream (Patent Document 3). Furthermore, there is a technique of containing an ionic active agent for improving the free fluidity of the obtained preparation, preventing moisture absorption during storage, and preventing enzyme deactivation (Patent Document 4). There is also a technique of improving the stability of an enzyme in an aqueous solution by chemically modifying the enzyme with a water-soluble polymer and then adding a surfactant and a boric acid compound (Patent Document 5).
Japanese Patent Publication No.41-152 JP-A-61-108387 Japanese Examined Patent Publication No. 4-82040 Japanese Patent Laid-Open No. 10-204494 JP 2000-17299 A

In the conventional technique for producing the above-mentioned enzyme granules, the present inventor suppresses inactivation of the enzyme until the step of preparing a powdered enzyme preparation from the enzyme-containing solution (Patent Documents 1 and 2). In the process of granulating using a powdered enzyme preparation (Patent Documents 3 and 4), a problem was found that enzyme inactivation could still occur. If the enzyme is deactivated, the enzyme-containing granulated product cannot exhibit the performance as a cleaning agent, and the commercial value is lowered.
Accordingly, an object of the present invention is to provide a method for producing a highly active enzyme-containing granulated product by suppressing inactivation of the enzyme even when the enzyme is granulated.

  As a result, the inventors of the present invention have found that when the enzyme powder is granulated, the enzyme is deactivated by being exposed to a certain high temperature and / or high share for a long time. In addition, as a result of studying the components and methods for preventing the deactivation, the step of drying the enzyme solution to form a powdered enzyme preparation and / or the step of granulating the obtained powdered enzyme preparation were carried out using an amino acid and its It has been found that an enzyme-containing granulated product can be produced without reducing the enzyme activity by carrying out the reaction in the presence of one or more selected from salts.

That is, this invention is a manufacturing method of the enzyme containing granulated product which has the process of following (A) and (B), Comprising: The process of (A) and / or (B) is carried out from an amino acid and its salt. The present invention provides a method for producing an enzyme-containing granulated product that is carried out in the presence of one or more selected types.
(A): A step of drying an enzyme-containing solution to form a powdered enzyme preparation (B): A step of dry granulating the powdered enzyme preparation obtained in step (A)

  By the method of the present invention, enzyme inactivation can be suppressed even when the enzyme is granulated, and a highly active enzyme-containing granulated product can be obtained.

  Although the enzyme in this invention will not be restrict | limited especially if it is an enzyme which mix | blends with detergent and exhibits an effect, 1 type, or 2 or more types chosen from protease, esterase, and carbohydrase are used preferably. Specific examples of protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, papain, aminopeptidase, carboxypeptidase and the like. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like. Examples of carbohydrase include cellulose, maltase, saccharase, amylase, pectinase, α- and β-glycosidase. Among these, it is preferable to use a proteolytic enzyme, that is, protease, from the viewpoint of the effect of inhibiting enzyme deactivation during enzyme granulation. The content of the enzyme in the enzyme-containing granulated product is not particularly limited, but is generally 0.01 to 30% by mass (hereinafter simply referred to as “%”) in view of the effect when blended with a detergent. ) Is preferable, and more preferably 1 to 30%.

  In the present invention, it is necessary to perform the operation in the presence of one or more selected from amino acids and salts thereof (when all are included, they are simply described as “amino acids etc.” hereinafter). The phrase “in the presence of one or more selected from amino acids and salts thereof” includes the case where one or more selected from amino acids and salts thereof are produced in the production process. Examples of amino acids include glycine, alanine, lysine, glutamic acid, aspartic acid, and examples of the salt include sodium salt, potassium salt, and magnesium salt. From the viewpoint of the effect of inhibiting enzyme deactivation during enzyme granulation. Moreover, in this invention, in order to produce | generate 1 type, or 2 or more types selected from an amino acid and its salt in a manufacturing process, the protein which does not have enzyme ability, or its degradation product can be used. In this case, it is preferable to use a protease as the enzyme from the viewpoint that these components are decomposed by the protease to produce amino acids. Proteins derived from various animals and plants can be used as the protein having no enzyme ability or a degradation product thereof. For example, collagen-derived proteins or soybean protein can be used.

  Collagen is a fibrous, sparingly soluble substance present in animal bones, cartilage, tendons, skin, fish scales, etc., but this is pretreated with acid or alkali and then heated to break down the molecular structure and solubilize. In addition, gelatin is preferable from the viewpoint of the enzyme deactivation suppression effect during enzyme granulation.

  Furthermore, a collagen peptide obtained by further degrading gelatin by a method such as enzymatic degradation can also be used.

  Soy protein is a protein contained in dried soybeans by about 30 to 35%, and is produced from defatted soybeans after extraction of soybean oil from soybeans. Moreover, since the soybean peptide which is the enzyme degradation product or fermentation product exists as an oligopeptide with an average number of 3 to 6 amino acids, it is excellent in solubility.

  In the present invention, the step (A) requires a step of drying the enzyme-containing solution to obtain a powdery enzyme preparation. The amino acid and the like in the enzyme solution is preferably 5 to 100 parts with respect to 100 parts by mass of enzyme solids (hereinafter simply referred to as “parts”) from the viewpoint of the effect of inhibiting enzyme inactivation, and more preferably 10 to 10 parts. It is preferable that it is 70 parts, especially 20-50 parts.

  In the present invention, it is preferable from the viewpoint of physical properties of the powdered enzyme preparation after drying that an ionic surfactant is contained in the enzyme solution. Among the ionic surfactants, anionic surfactants include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate (AES), alkyl or alkenyl sulfate (AS), olefin sulfonate (AOS), and alkanesulfone. Acid salt, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfo fatty acid salt or ester, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl or alkenyl phosphate ester or salt thereof , Polyoxyethylene alkyl ether sulfate salts, carboxylic acid type polymer surfactants, and the like. Examples of amphoteric surfactants include alkylbetaines, alkylamine oxides, carboxy or sulfobetaine surfactants. Examples of the cationic surfactant include quaternary ammonium salts having a mono- or di-long chain alkyl group. The content of the ionic surfactant is 0.01 to 0.5 part with respect to 100 parts of the enzyme solid content, which improves the physical properties of the powdered enzyme preparation after drying, the enzyme deactivation inhibiting effect From the above point, it is preferable that the content be 0.03 to 0.3 part, particularly 0.05 to 0.2 part.

  In the present invention, a diluent for keeping the enzyme activity constant when the powdered enzyme preparation is prepared can be blended in the enzyme solution as necessary. Examples of the diluent include sulfates, halides, carbonates, phosphates, silicates, boric acid or salts thereof, saccharides, and the like. It is preferable that the compounding quantity of a diluent is 50-300 parts with respect to 100 parts of enzyme solid content from the point of operativity in a process (B) and cost.

  More specifically, examples of the sulfate include sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, ferrous sulfate, sodium thiosulfate, aluminum sulfate halide, and the like as sodium chloride, potassium chloride. , Calcium chloride, magnesium chloride, potassium bromide, etc., carbonates include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, etc., phosphates include sodium phosphate, sodium hydrogen phosphate , Sodium dihydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, sodium pyrophosphate and the like, and silicates include sodium silicate, sodium metasilicate, potassium silicate, calcium silicate and the like, As boric acid or its salt C sand, potassium borate, boric acid. All monosaccharides as sugar, all disaccharide, for example lactose, maltose, and trehalose. These can be used individually by 1 type or in mixture of 2 or more types.

  In the present invention, it is necessary to prepare an enzyme solution and then dry it to obtain a powdered enzyme preparation. Spray drying is preferred as the drying means. In order to produce a powdery enzyme preparation by spray drying, the enzyme solution can be dried using a normal spray dryer. There are two types of spray dryers, the nozzle type and the disk type, which can be used properly when it is necessary to control the particle size of the powdered enzyme preparation. A nozzle type is preferred when producing a preparation with a small particle size (1 μm or less), and a disk type is preferred when producing a formulation with a large particle size.

  The hot air temperature in the spray dryer is preferably 100 to 200 ° C., more preferably 130 to 170 ° C., and the exhaust air temperature is preferably 50 to 100 ° C., and more preferably 60 to 100 ° C. From the point of view, it is preferable.

  In the present invention, as a method for performing the drying in the step (A) in the presence of an amino acid or the like, the amino acid or the like may be dissolved in contact with the enzyme solution in advance, before, after or simultaneously with the addition of the diluent. Either is fine.

  In the present invention, as the step (B), a step of dry granulating the powdered enzyme preparation obtained in the step (A) is necessary. Dry granulation means a granulation method that does not use water as a binder. In this case, the water content in the granulator is 0 to 10%, more preferably 0 to 5%, especially 0 to 3%. From the viewpoint of inhibiting enzyme deactivation during granulation. Examples of the granulation operation include extrusion granulation, rolling granulation, pulverization granulation, fluidized bed granulation, spray granulation, and pulverization granulation. Among these, the tumbling granulation method, particularly the stirring tumbling granulation method, is preferable from the viewpoint of granulation yield and the suppression of enzyme deactivation during granulation. In dry granulation, it is preferable to use a core substance and a binder as additives in addition to the powdered enzyme preparation. Moreover, it is preferable from a soluble point of an enzyme containing granulated material that all are water-soluble.

  Examples of the water-soluble nuclear material include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, sugar and the like. The average particle diameter of the water-soluble nuclear material is preferably 200 to 1200 μm, more preferably 350 to 850 μm, and particularly preferably 425 to 700 μm from the viewpoint of granulation yield. Further, those having a particle diameter of 200 μm or less are preferably 10% or less, more preferably 5% or less, particularly preferably 3% or less, and those having a particle diameter of 1200 μm or more are 5% or less, more preferably 3% or less, particularly 1%. The following is preferable from the same point. In addition, it is preferable from the same point that the water-soluble nuclear substance has an average particle size in the range of 350 to 850 μm and is 85% or more, and further in the range of 425 to 700 μm is 80% or more.

  As the water-soluble binder, use of a water-soluble organic binder having a melting point or a softening point of 25 to 90 ° C. suppresses caking of the granulated product during storage, solubility of the granulated product, enzyme deactivation during granulation It is preferable from the viewpoint of suppression. The melting point or softening point is preferably 30 to 80 ° C., more preferably 35 to 70 ° C. from the same point. Specific examples of the substance include (a) polyethylene glycol or a derivative thereof, a water-soluble polymer selected from the group consisting of polyoxyethylene-polyoxypropylene glycol copolymers, and (b) nonionics such as polyoxyethylene alkyl ether. Surfactants, (c) polycarboxylic acid salts having an average molecular weight of 4000 or more, and the like, and one or a mixture of these can be used. Among these, polyethylene glycol is preferable from the viewpoint of solubility of the enzyme-containing granulated product.

  The amount of water-soluble organic binder used is unclear because there are differences in the properties of each binder, but in order to increase the enzyme activity of the resulting enzyme granulation as much as possible, the binder effect is manifested in as little amount as possible. Is generally preferred. Therefore, these water-soluble organic binders are preferably contained in the enzyme-containing granulated product in an amount of 5 to 50%, more preferably 10 to 30%.

  In the present invention, the method of performing the step (B) in the presence of an amino acid or the like may be carried out by dry granulation by mixing the amino acid or the like in the form of other raw materials in the form of powder, and the order of addition is not particularly limited. .

  In the present invention, by performing either one of steps (A) or (B) or both steps (A) and (B) in the presence of an amino acid or the like, the enzyme is lost during step (B). Although the effect which suppresses activity is acquired, it is preferable from the point of the said effect to perform a process (A) in presence of an amino acid etc. In addition, from the viewpoint of good powder physical properties (low angle of repose) and easy operation in the production process, step (A) is not performed in the presence of amino acids and the like, but only step (B) is present of amino acids and the like. It is preferable to carry out below. Moreover, it is preferable from the point of operativity of a process (B) to perform a process (A) and a process (B) in the presence of an amino acid.

  In the present invention, a powdery extender can be further added as necessary during granulation. As the extender, it is preferable to use one or more inorganic salts selected from the group consisting of sulfates, carbonates and hydrochlorides of alkali metals or alkaline earth metals. Of these, water-soluble inorganic alkali metal salts such as sodium sulfate, sodium carbonate, and sodium chloride are preferred because they do not affect the cleaning performance. Examples of other extenders include water-soluble organic acid salts such as sodium citrate, talc, titanium oxide, calcium carbonate, zeolite, magnesium carbonate, activated clay, kaolin, diatomaceous earth, bentonite, perlite, and acid clay.

  Furthermore, in the present invention, it is also possible to use various inorganic salts such as calcium salts and magnesium salts, or organic substances such as surfactants, sugars and carboxymethylcellulose. In addition, pigments, dyes and pigments can be blended to color enzyme granules.

  The above-mentioned stirring tumbling granulator generally has a main stirring shaft provided with stirring blades at the center, and further has an auxiliary stirring shaft for assisting mixing and suppressing the generation of coarse particles. It protrudes from the wall surface in the direction perpendicular to the stirring shaft. As a stirring rolling granulator having such a structure, Henschel mixer (Mitsui Miike Chemical Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.) A vertical granulator (Fuji Sangyo Co., Ltd.) can be mentioned. Examples of the main stirring shaft installed horizontally include a Redige mixer (Matsuzaka Giken Co., Ltd.), a pro shear mixer (Pacific Kiko Co., Ltd.), etc., and any of them may be used in the present invention.

  The particle size of the enzyme-containing granulated product obtained by the granulation step is not particularly limited, but the average particle size is 200 to 3000 μm, and more preferably in the range of 350 to 1000 μm. It is preferable from the viewpoint of solubility.

  The enzyme-containing granulated product produced by the method of the present invention can be used without coating, but coating is preferable because the storage stability of the enzyme is further improved. The coating agent for the enzyme-containing granulated product is not particularly limited, but is a water-soluble film-forming polymer such as polyethylene glycol, polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivative, starch derivative; these polymers and talc, clay And water-soluble or sparingly soluble inorganic particles such as titanium oxide and calcium carbonate, or a combination with a protective agent such as alkali metal silicate and alkali metal carbonate. The coating agent is preferably 0.01 to 0.7 part, more preferably 0.05 to 0.6 part with respect to 100 parts of the enzyme-containing granulated product, from the viewpoint of improving the storage stability of the enzyme.

  Examples of the coating method include a method of coating by a conventional method using an apparatus such as a fluidized bed granulator, a coating pan granulator, and a stirring granulator.

  The enzyme-containing granulated product produced by the method of the present invention is useful as a blending component of a cleaning composition, and the cleaning composition containing this is used as a cleaning agent for clothing, tableware, residential use, etc. Can be used.

Examples 1 to 9, Comparative Example 1 and Reference Example [Production of powdered enzyme preparation (step (A))]
A protease (4.5% enzyme solid content) solution derived from Bacillus sp. KSM-9865 (FEM-P18566) (quaternary ammonium salt (Cotamine 60W, Kao Co., Ltd.)) was added in 0.1 parts to 100 parts enzyme solid content. In addition, sodium sulfate was blended as a diluent, and an amino acid solution shown in Table 1 was blended or not blended to prepare an enzyme solution. The obtained enzyme solution was spray-dried with an atomizer spray dryer at an atomizer rotational speed of 12,000 r / min, a hot air temperature of 165 ° C., and an exhaust air temperature of 75 ° C. to obtain a powdered enzyme preparation. The active yield of the obtained powdered enzyme preparation is shown in Table 1. Alanine was β-alanine, gelatin was “Gelatin R” (Nitta Gelatin Co., Ltd.), and soy protein was “New Fuji Pro-AE” (Fuji Oil Co., Ltd.).

[Production of enzyme-containing granulated product (step (B))]
Formulated with 11% of the powdered enzyme preparation produced by the above method, 55% sodium chloride as the water-soluble core substance, 5% polyethylene glycol 6000 (Kao Co., Ltd.) and 29% sodium sulfate as the water-soluble organic binder. For Examples 8 and 9, powdered amino acids were blended in the amounts shown in Table 1. Sodium chloride having an average particle diameter of 610 μm, 3% of particles of 200 μm or less, and 0% of particles of 1200 μm or more was used.
Next, 3.75 kg of the raw material of the above composition was put into a high speed mixer FS-5 type (Fukae Kogyo Co., Ltd.), and agitator was stirred at 540 r / min and chopper 900 r / min while flowing 90 ° C. warm water through the jacket. Mixing was performed and the contents were raised to 88 ° C. Thereafter, the hot water was stopped, cooling water was allowed to flow through the jacket, and air was blown into the mixer to cool to 54 ° C. In addition, the enzyme containing granulated material was obtained by granulation operation about 1 hour and 15 minutes from raw material addition. The active yield of the obtained enzyme-containing granulated product is shown in Table 1.

[Calculation method of activity yield]
Activity yield in step (A) = (protein specific activity of powdered enzyme preparation / protein specific activity of enzyme solution) × 100 (%)
Activity yield in step (B) = (protein specific activity of enzyme-containing granulated product / protein specific activity of powdered enzyme preparation) × 100 (%)

[Measurement of repose angle]
Using a powder tester (Hosokawa Micron Co., Ltd.), measurement was performed according to a conventional method. That is, the powdered enzyme preparation was placed on a standard sieve (mesh opening 710 μm), and the sieve was vibrated to cause the powdered enzyme preparation to flow out via a funnel and dropped onto a measurement table. Thereafter, when the angle of repose reached a certain level, the flow of powder was stopped and the angle of repose was measured.

  From the results shown in Table 1, when an amino acid or the like is added to the step (A) and / or (B) and the treatment is performed, the deactivation of the enzyme in the enzyme-containing granulated product production step is remarkably suppressed. It was. In addition, when no amino acid or the like was blended in the step (A) but only in the step (B), the powder physical properties indicated by the angle of repose were good. Furthermore, when an amino acid etc. is mix | blended with process (A) and (B), active yield is favorable, the operativity of process (B) is favorable, and the granulated material with a uniform particle size is obtained. It was.

Claims (3)

A method for producing an enzyme-containing granulated product having the following steps (A) and (B), wherein the step (A) and / or (B) is selected from amino acids and salts thereof: The manufacturing method of the enzyme containing granulated material performed in presence of 2 or more types.
(A): a step of drying the enzyme-containing solution to obtain a powdered enzyme preparation (B): a step of dry granulating the powdered enzyme preparation obtained in step (A)   The method for producing an enzyme-containing granulated product according to claim 1, wherein the enzyme is a protease.   The method for producing an enzyme-containing granulated product according to claim 1 or 2, wherein the dry granulation is stirring tumbling granulation.