JPH1023888A - Production of granulated enzyme - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a granulated enzyme having uniform grain size and useful for detergents, bleaching agents, etc., by mixing granulation components comprising a thermoplastic water soluble binder having a melting point or a softening point in a specific range, an enzyme and no water and extruding the mixed components at a higher temperature than the melting point or the softening point of the binder. SOLUTION: This granulated enzyme having uniform grain size is produced by mixing components for granulation containing an enzyme, 10-40wt.% of thermoplastic water soluble binder having 35-80 deg.C melting point or softening point such as polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene phenol ether and essentially no water, extruding the mixture at a higher temperature than the melting point or the softening point of the thermoplastic water soluble binder, sphering the extruded product to have 100-200% average sphericity and coating the extruded or sphered extruded product to have <=200μm coated thickness by an agitating and rolling granulation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an enzyme granulated product. More specifically, the present invention relates to a method for producing an enzyme granulated product in which an enzyme-containing powder is formed into a granulated product having a uniform particle size while minimizing a decrease in enzyme activity. The enzyme granules are used for detergents, bleaching agents, bath agents, etc., and are also used as meat softeners, rice cooking enzyme agents, and feed addition enzyme agents.

[0002]

2. Description of the Related Art Many studies have been made on granulation methods of raw enzyme powders. For example, as a wet granulation method in which water is added as a binder during compaction molding, Japanese Patent Publication No.
JP-A-49554 discloses a method of extrusion molding using 3 to 25% water, and JP-A-57-137400 discloses an extrusion molding method using water while maintaining the lubricity of the raw enzyme powder with polyacrylamide. To do, EP 5644
In JP-A-76-76, there is a method of extruding an enzyme bulk using water while maintaining lubricity with a water-soluble organic polymer.

However, in these methods, since water is used as a binder, a drying operation after granulation is indispensable in order to secure storage stability and improve product properties. In this case, to avoid deactivation of the enzyme during storage, it is necessary to dry it to a low moisture area, so drying the granulated particles requires a high drying energy and a large heat history given to the enzyme. Not preferred.

On the other hand, as a non-aqueous granulation method which does not require drying in the granulation operation of the raw enzyme powder, it is generally considered that extrusion molding is difficult due to inactivation of the enzyme due to heat generation from the screen. Dynamic granulation is commonly used. For example, WO 87/04184 discloses a method in which a mixture of a raw enzyme powder and a wax as a binder is heated to a temperature equal to or higher than the melting point of the wax to perform agitated tumbling granulation. However, in this method, there is a problem that the particle size distribution of the granulated material is widened due to the use of the stirring tumbling granulation method, the yield is reduced, and the classification is performed during the compounding of the enzyme granulated material. In rolling granulation from fine powder without using nuclei, special consideration is required for the composition in order not to cause in-machine adhesion, which causes a problem that the flexibility of the granulated composition is reduced.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an enzyme preparation which suppresses a decrease in enzyme activity, is difficult to classify when blended in a detergent or the like, has a narrow particle size distribution, and has a high degree of freedom in composition. An object of the present invention is to provide a method for producing granules. It is a further object of the present invention to provide a detergent composition containing the enzyme granules obtained by such a production method.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies for the purpose of granulating and granulating the enzyme powder having low heat stability without inactivating the enzyme powder. Using a thermoplastic water-soluble binder as a binder and a lubricant,
In the case of extrusion molding, surprisingly, it has been found that even in a non-aqueous system, heat generation in an extrusion screen can be suppressed, and an enzyme granulated product having a small particle size with little enzyme deactivation can be obtained at a low energy cost. .

That is, the gist of the present invention is as follows: [1] Step a: melting point or softening point is 35 to 80 ° C.
Containing 10 to 40% by weight of a thermoplastic water-soluble binder,
Mixing an enzyme-containing granulation component substantially free of water, step b: extruding the mixture obtained in step a at a temperature equal to or higher than the melting point or softening point of the thermoplastic water-soluble binder. [2] a method wherein the thermoplastic water-soluble binder is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene phenol ether; [3] The method according to [1] or [2], further comprising the step of: c) cooling the extruded product obtained in step b. [4] The above-mentioned [1] to [3], further comprising a step d: a step of spheroidizing the extruded product obtained in the step b or the step c. The method of manufacturing deviations or wherein the average sphericity of the extrudate which is [5] spheronization 100
The method according to the above [4], wherein the step e is a step of coating the extruded product or the extruded product obtained in the step b, the step c, or the step d. The manufacturing method according to any one of the above [1] to [5], wherein [7] the extruded product or the spherical extruded product is coated by stirring and rolling granulation. [8] The method according to [6] or [7], wherein the thickness of the coating layer is 200 μm or less,

[9] The composition of the above-mentioned [6]-, wherein the composition of the coating layer contains 20 to 95% by weight of the poorly water-soluble powder and 5 to 30% by weight of a thermoplastic water-soluble binder having a melting point or softening point of 35 to 80 ° C.
[8] The method of any one of [1] to [1].

[9] A detergent composition obtained by mixing an enzyme granulated product obtained by any one of the production methods and a detergent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an enzyme granulated product of the present invention comprises the steps of: Step a: comprising substantially 10 to 40% by weight of a thermoplastic water-soluble binder having a melting point or a softening point of 35 to 80 ° C. Mixing the enzyme-containing granulated component not containing, and step b: extruding the mixture obtained in step a at a temperature equal to or higher than the melting point or softening point of the thermoplastic water-soluble binder. Steps c to g depending on
Up to and including each step. Hereinafter, each step will be described in order.

(1) Step (a) In step (a), an enzyme-containing granulation component containing 10 to 40% by weight of a thermoplastic water-soluble binder having a melting point or softening point of 35 to 80 ° C. and containing substantially no water is mixed. This is the step of performing
Here, examples of the enzyme-containing granulating component include a raw enzyme powder, a thermoplastic water-soluble binder having a melting point or a softening point of 35 to 80 ° C, and various additives. The enzyme-containing granulated component in the present invention does not substantially contain water in order to make a drying operation unnecessary after granulation. The term “substantially free of water” as used herein means a water content of 3% by weight or less in the whole enzyme-containing granulated component. Such a water content is preferably 2.5% by weight or less, more preferably 2.0% by weight.
It is as follows. With such a degree, granulation can be performed without drying. Therefore, the amount of water in the bulk enzyme is
There is no particular limitation as long as the moisture in the enzyme-containing granulated component falls within a predetermined range. The amount of water in the enzyme-containing granulated component can be determined, for example, by measuring the amount of water released while maintaining in a 105 ° C. atmosphere for 60 minutes.

A) Enzyme bulk The enzyme bulk used in the present invention is generally obtained by filtering and filtering an enzyme produced by a microorganism, and may contain various components depending on the culture and separation conditions. Specifically, it is a stabilizer, sodium sulfate, impurities, water and the like. In addition, enzyme bulk powder,
PEG obtained not only in the form of a dry powder but also by a method such as aqueous two-phase distribution described in JP-A-8-41491
(Polyethylene glycol) may be a bulk enzyme containing a large amount of (polyethylene glycol). The PEG contained in this case is treated as a thermoplastic water-soluble binder having the following melting point or softening point of 35 to 80 ° C.

The enzyme used in the present invention is not particularly limited, and includes, for example, one or more enzymes selected from the group consisting of proteases, esterases and carbohydrases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, splicitin, papain,
Examples include aminopeptidase, carboxypeptidase and the like. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, phosphatases, and the like. Examples of carbohydrase include cellulase, maltase, saccharase, amylase, pectinase, α- and β-glycosidase.

In the present invention, the amount of the raw enzyme powder is not particularly limited, but is preferably 3 to 90% by weight, more preferably 10 to 60% by weight in the enzyme-containing granulated component. It is particularly desirable that the content be 15 to 50% by weight. If it is less than 3%, the absolute amount of the bulk powder is too small, so that the reliability of the mixture may be low. Further, from the viewpoint of blending a thermoplastic water-soluble binder that gives sufficient lubricity to the granulated component mixture, 90% by weight is used.
The following is preferred.

B) Thermoplastic water-soluble binder having a melting point or softening point of 35 to 80 ° C. Examples of such a binder include a water-soluble polymer and a nonionic surfactant. Examples of the water-soluble polymer include polyethylene glycol and polypropylene glycol. Examples of the nonionic surfactant include polyoxyethylene alkyl ether and polyoxyethylene phenol ether. One of these thermoplastic water-soluble binders may be used alone, or two or more of them may be used in combination.

The thermoplastic water-soluble binder used in the present invention has a melting point or softening point of 35 to 80 ° C., preferably 45 to 70 ° C., more preferably 50 to 70 ° C.
Particularly preferred is a temperature of -65 ° C. The melting point or the softening point is preferably 35 ° C. or higher in order to prevent deterioration of physical properties due to melting or softening of the binder during storage, and is preferably 80 ° C. or lower from the viewpoint of suppressing enzyme deactivation during the granulation operation. In the present invention, the melting point is determined according to Japanese Industrial Standard J.
It is measured by the melting point measurement method described in IS-K0064 (1192). The softening point is also determined by the above JIS-K0064 (119)
2) Measure by the melting point measurement method described.

The purpose of blending the thermoplastic water-soluble binder is as follows:
It is used as a binder and a lubricant, and its blending amount needs to be adjusted depending on the oil absorbing ability of the powder composition, but is 10 to 40% by weight, preferably 13 to 40% by weight in the enzyme-containing granulated component.
Its performance can be achieved in the range of 30% by weight, more preferably 15 to 25% by weight. If the compounding amount is less than 10% by weight, not only poor molding of the extrudate and deterioration of performance but also heat generation due to resistance on the extrusion screen may occur, which may promote the deactivation of the enzyme. When the amount is more than 40% by weight, noodles extruded from the screen coalesce with each other, although the heat generation during extrusion is small, so that it may be difficult to obtain a noodle-shaped product.

C) Various additives In the enzyme-containing granulating component of the present invention, known substances that do not adversely affect the stability of the enzyme include extenders, diluents, solubilizers, disintegrants, lubricants, It can be further appropriately compounded as a pigment, a dye, a fragrance or the like. For example, inorganic salts, water-insoluble fine powder, cereal powder, cellulose derivatives and the like can be mentioned. Examples of the inorganic salts include sodium sulfate, magnesium sulfate, calcium sulfate, sodium chloride, potassium carbonate and the like. Examples of the water-insoluble fine powder include talc, clay, silica, alumina, kaolin and the like. Grain flour includes starch, flour, sugar and the like. Examples of cellulose derivatives include microcrystalline cellulose, low-substituted hydroxypropylcellulose (L-HPC),
Carboxymethyl cellulose (CMC) and the like. Among them, sodium sulfate (sodium sulfate) is preferably used because it has good solubility in water and also works as a dispersant.
The amount of such a bulking agent and the like must be comprehensively determined from the activity value of the raw enzyme powder, the desired activity as a granulated product, the bulk of the raw powder, the oil absorbing ability, and the like. % By weight or less, more preferably 20 to 70% by weight.

D) Mixing method The method of mixing the enzyme powder, the thermoplastic water-soluble binder, and various additives to be added as required is not particularly limited. At the start of mixing, the thermoplastic water-soluble binder may be in a solid state or a liquid state. It may be any, but at least at the end of extrusion, preferably at the end of mixing, that the thermoplastic water-soluble binder is sufficiently melted or softened, that it is sufficiently mixed, and that the enzyme has an unnecessarily high heat history. It is important not to give to. Therefore, for example, the following aspects are considered. Finally, in the case of using an enzyme bulk powder that has undergone a drying step, a solid thermoplastic water-soluble binder, a bulking agent, etc. are blended / mixed with the bulk powder immediately after drying, and the thermoplastic aqueous solution is sensitized by the sensible heat of the enzyme bulk powder. Embodiment in which the hydrophilic binder is melted or softened. An embodiment in which a raw enzyme powder, a solid thermoplastic water-soluble binder, an extender, and the like are blended / mixed, and heat is externally applied to melt or soften the thermoplastic water-soluble binder. A mode in which a thermoplastic water-soluble binder is previously melted or softened, and a liquid binder is mixed with an enzyme powder, an extender, and the like. The mixer used for mixing the above components is not particularly limited. For example, a Nauter mixer (manufactured by Hosokawa Micron Corporation), a V-type blender (manufactured by Corporation)
Dalton), high-speed mixer (Fukae Kogyo Co., Ltd.)
Henschel Mixer (Mitsui Miike Mine Co., Ltd.),
Redige mixer (made by Redige) and the like.

(2) Step b Step b is a step of extruding the mixture obtained in step a at a temperature equal to or higher than the melting point or softening point of the thermoplastic water-soluble binder. The extrusion granulator used here is not particularly limited, but includes a pelletizer double, a twin dome gran, a disk pelleter (manufactured by Fuji Paudal Co., Ltd.),
Basket type granulator (manufactured by Kikusui Seisakusho), granulizer (manufactured by Hosokawa Micron Corporation) and the like.
Thus, a cylindrical extruded product having a diameter of 200 to 3000 μm can be obtained. Such an extruded product can be used as it is as an enzyme granulated product, but depending on the required form of the product, it may be appropriately subjected to any subsequent step (step c to step g).

(3) Step c Step c is a step of cooling the extruded product obtained in step b. Cooling the extruded product is preferable because coalescence and agglomeration of the formed product can be suppressed. As a method of cooling the extruded product, a method of cooling may be used. However, industrially, there is a method of blowing cold air using a vibration conveyor, a fluidized bed or the like. In the case where the extruded product is crushed and spheroidized in the next step d, the cooling step can be performed simultaneously with a crushing / sphering machine. Examples include Malmerizer (Fuji Paudal Co., Ltd.) and Spiral Flow (Freund Sangyo Co., Ltd.)
Manufactured by Mitsui Mining Co., Ltd., and a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.).

(4) Step d Step d is a step of spheroidizing the extruded product obtained in step b or step c. Although the enzyme granules themselves may be used as the product, preparing the product form by crushing the extruded enzyme-containing granules and performing operations such as spheroidization and classification is a measure against It has advantages such as dust control and improved appearance, and can add value to the product. When a coating is applied to improve the stability of the extruded granules, the sphericity of the extruded granules serving as core particles is important. When a sphering operation is performed for this purpose, it is desirable to increase the sphericity. That is, by increasing the sphericity of the core particles, the efficiency of the powder coating in the next step is increased, and high stability in the compounded product is provided.
The average sphericity of the granules obtained by the sphering operation is
Preferably 100-200%, more preferably 100-200%
170%. Further, the sphericity distribution of each of the extruded spheroidized products is preferably in the range of 100 to 220%, 70% or more, preferably 80% or more, more preferably 90% or more of the total number. If the average sphericity exceeds 200%, the coating thickness tends to be non-uniform when powder coating is performed by agitating tumbling granulation, which is not preferable. Here, the sphericity is represented by the following equation. Sphericity = (Area of circle with diameter equal to longest width of projected view / projected area) × 100%) The average sphericity is a value obtained by N = 1000. The object of the sphericity measurement is an extruded product, and the fragments (fine powder) generated during the sphering process are excluded from the measurement object.

For crushing and spheroidization, generally known methods can be used. For example, the disintegration includes Fitzmill (Fitzpatrick Co., USA), Comminator (Fuji Paudal Co., Ltd.), Speed Mill (Fuji Paudal Co., Ltd.), etc. The temperature supplied to the disintegrator Is preferably cooled to around room temperature, so that adhesion to the crusher is suppressed.The spheroidization is performed by using a spiral flow (made by Freund Sangyo Co., Ltd.) made by Malmerizer (Fuji Paudal Co., Ltd.) In addition, in these devices, the crushing operation may also be performed.In the agitating tumbling granulator described later, the crushing / spheroidizing process is also performed in the same model as a preliminary operation of the agitating tumbling operation. Can be done with

(5) Step e Step e is a step of coating the extruded or spherical extruded product obtained in step b, step c or step d. The coating step is preferred because storage stability when blended into a product is improved and sufficient enzyme activity is maintained even in a product blended with a destabilizing component such as a bleaching agent. This coating step can be carried out by using a granulating agent and a water-soluble binder, preferably by stirring and rolling. a) Granulating agent Any component can be used as long as it does not reduce the enzyme activity. For example, hydrophilic powder, water-insoluble or poorly water-soluble powder can be used. As the hydrophilic powder, sodium chloride,
Calcium chloride, sodium sulfate, sugar and the like, as water-insoluble or poorly water-soluble powder, talc, titanium oxide, calcium carbonate, zeolite, magnesium carbonate, activated clay,
Kaolin and the like. These powders preferably account for at least 50%, preferably at least 70%, of the composition of the coating layer in order to keep the thickness of the coating layer constant while minimizing the pressure on the composition and the decrease in solubility. Among them, talc, titanium oxide, and the like, which are water-insoluble or hardly water-soluble powders, are effective because they form a dense structure on the surface of the granulated substance and prevent the invasion of moisture that causes the deactivation of enzymes.

B) Water-soluble binder As the binder used for coating, a film-forming polymer (such as hydroxymethylcellulose) can also be used. In the case of coating using these, 30% by weight of a solvent such as water is used. Dissolve in a concentration less than
This requires spray coating and drying with a fluidized bed or the like, which is disadvantageous in terms of equipment costs and energy costs. Therefore, in the coating operation, it is more preferable to perform coating by stirring and rolling granulation using a thermoplastic water-soluble binder having a melting point or a softening point of 35 to 80 ° C as a binder. Also,
The thermoplastic water-soluble binder used for the coating is more preferably a thermoplastic water-soluble binder having a melting point or a softening point lower than 0 to 10 ° C. than the binder used when preparing the enzyme granules to be the core particles used in steps a and b. . This is because the core particles do not start softening in the rolling granulation operation.

C) Stirring Rolling Granulator As specific examples of the stirring rolling granulator, Henschel mixer (Mitsui Miike Kakoki Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator ( Fuji Sangyo Co., Ltd., Gakuo (Mitsui Mining Co., Ltd.), Ladyge Mixer (Ladyge), Aqua Coater (Freund Corporation), and the like. In addition, the spheroidizing step of the step d and the step e can be carried out in the same agitating tumbling granulator.
In this case, capital investment costs are lower than in a case where independent devices are provided for each process, which is preferable in terms of manufacturing costs.

The thickness of the coating layer formed by this coating step is preferably 200 μm or less, and
It is more preferred that: The thickness of the coating layer is 200
If it exceeds μm, the solubility will decrease, and it will be difficult to express sufficient enzyme activity. When the coating thickness is large, it is difficult to obtain a material having a sharp particle size distribution. In the present invention, an enzyme granulated product (extruded product) having a narrow particle size distribution is obtained in step b, and thus has a feature that the thickness of the coating layer is uniform.
The binder in the composition of the coating layer is a thermoplastic water-soluble binder having a melting point or a softening point of 35 to 80 ° C.
It is preferred to contain 0% by weight.

(6) Step f Step f is a step of cooling the coating obtained in step e. The cooling reduces the adhesiveness of the coating and increases the particle strength, so that the products can be prevented from coalescing and deforming during transportation. Examples of the apparatus that can be used in this step include a vibrating conveyor and a fluidized bed. When a stirring and rolling granulator is used in the coating step, the apparatus can also be used by switching the jacket temperature.

(7) Step g Step g is a step of classifying the molded product obtained in step b, step c, step d, step e, or step f. By cutting fine powder and coarse powder generated in each step by classification, the particle size becomes more uniform, and problems such as classification in products and dust generation during use are suppressed. As an apparatus used in this step, a Kotobuki circular vibrating sieve (manufactured by Tokuju Corporation) and the like can be mentioned.

Through the above steps, an enzyme granulated product in which a decrease in enzyme activity is suppressed can be produced. The enzyme granulated product obtained by the method of the present invention has a particularly narrow particle size distribution as compared with the case of stirring and tumbling granulation from a fine powder material, so that it is difficult to classify even when blended in a detergent or the like. In addition, it is not necessary to make the composition particularly considering the adhesion in the machine, so that the degree of freedom of the composition can be increased.

The enzyme granules obtained by the production method of the present invention can be used as additives in many detergents. Therefore, the detergent composition of the present invention refers to a mixture of the enzyme granules and other components generally used in detergents. The detergent composition of the present invention is used, for example, as a bleach detergent, an automatic dishwasher detergent, a clothing detergent, and the like. As other components to be mixed in addition to the enzyme granules, a surfactant as described below, an amorphous alkali metal silicate, a crystalline alkali metal silicate, a sequestering agent other than the crystalline alkali metal silicate, Alkaline agents, non-dissociated polymers, high-molecular builders such as organic acid salts, anti-fading agents, anti-staining agents, anti-caking agents, antioxidants, defoamers, bleaching agents, bleach activators, fluorescent dyes , Bluing agents, fragrances and the like.

The detergent composition of the present invention comprises an enzyme granulated product and the above-mentioned components.
One particle may be granulated, and the bleaching agent, bleaching activator, defoamer particles, some or all of the alkali agent or ion exchange agent, which will be described later, may be used as far as known in the art. It may be dry blended as three or more particles. The cleaning particles as a base can be produced by a known method. As for the bleaching detergent, granulated or eutectic materials obtained by adding a stabilizer such as a surfactant or a heavy metal scavenger to a hydrogen peroxide source such as PC (percarbonate) or PB (perborate). If necessary, a bleaching activator and, if necessary, an alkali agent such as a crystalline silicate or sodium carbonate are dry-blended. In addition,
When a PC is used, a known stabilizing method can be used.

The average particle size of the base detergent particles obtained by the above-mentioned production method according to JIS-K0069 (1192) is preferably from 200 to 1000 μm, more preferably from 300 to 800 μm. In addition, JIS K33
The bulk density of 62 is preferably 600 g / L or more, more preferably 700 to 1200 g / L.

Hereinafter, each component of the cleaning composition will be described in detail. Regarding the surfactant, the surfactant used in the detergent can be used without any particular limitation. Specifically, it is at least one selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants exemplified below.

Examples of the nonionic surfactant include the following. That is, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene glycol fatty acid alkyl ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid Esters, higher fatty acid alkanolamides, alkyl glucosides, alkyl glucose amides,
And alkylamine oxide.

Among them, it is particularly preferable to use polyoxyethylene alkyl ether as a nonionic surfactant from the viewpoint of cleaning performance, etc., and an average of 5 to 15 moles of ethylene oxide is added to an alcohol having an average of 10 to 18 carbon atoms. More preferred are those obtained by adding an average of 6 to 10 mol of ethylene oxide to an alcohol having an average of 12 to 14 carbon atoms.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid salt or ester salt, and alkyl or alkenyl ether carboxylate. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants, and the like, preferably alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylamine salt. Examples of the amphoteric surfactant include carboxy type and sulfobetaine type amphoteric surfactants.

The content of the surfactant is preferably 0.5 to 60% by weight in the detergent composition. More preferably, the content is 10 to 50% by weight in the case of a detergent for clothing, and 1 to 10% by weight in the case of a bleaching detergent and a detergent for an automatic dishwasher.

Regarding the crystalline alkali metal silicate The crystalline alkali metal silicate used in the detergent composition of the present invention has not only an alkali ability but also an ion exchange ability. The amount can be further reduced.

Further, the crystalline alkali metal silicate preferably has an average particle size of 1 to 60 μm, more preferably 1 to 30 μm. If the average particle size exceeds this range, the rate of onset of ion exchange tends to be slow, which causes a reduction in detergency.

As the crystalline alkali metal silicate used in the detergent composition, the alkali metal silicate SiO ₂ /
Preferably, M ₂ O (where M is an alkali metal) = 0.9 to 2.6, more preferably 1.5 to 2.2. If it is less than 0.9, the water resistance is insufficient and caking deterioration is likely to occur, and if it exceeds 2.6, both the alkali ability and the ion exchange ability are reduced, and the washing performance tends to deteriorate.

Among the crystalline alkali metal silicates used in the detergent composition, those having the following composition are preferred. _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (1) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.9 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (2) ( wherein, M represents an alkali metal, x '= 1.5~2.
6, y ′ = 0 to 20. )

First, the crystalline alkali metal silicate having the above composition will be described. In the general formula (1), M is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is selected from Group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, for example, Mg, Ca, Zn,
Y, Ti, Zr, Fe and the like can be mentioned. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more. For example, MgO, CaO
Like are mixed may constitute the Me _m O _n component.
Further, the crystalline alkali metal silicate of the present invention may be a hydrate, in which case the hydration amount is w =
It is in the range of 0-20.

In the general formula, y / x is 0.9 to 0.9.
2.6, and preferably 1.5 to 2.2. y /
When x is less than 0.9, the water resistance is insufficient and the physical properties of the powder of the detergent composition such as caking property and solubility are significantly adversely affected. If y / x exceeds 2.6, the alkalinity becomes low and becomes insufficient as an alkali agent, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger.
z / x is 0.01 to 1.0, preferably 0.02
0.9. When z / x is less than 0.01, the water resistance is insufficient, and when it exceeds 1.0, the ion exchange capacity is lowered and the ion exchange is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. As described above, when xM ₂ O is, for example, x′Na ₂ O · x ″ K ₂ O, x is x ′ + x ″. Such a relationship is represented by zMe
The same applies to z in the case _{where m} O _n component consist of two or more kinds. Also, n / m = 0.5 to 2.0
Represents the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 1.5, and 2.0.

The crystalline alkali metal silicate in the detergent composition contains M ₂ O, Si as shown in the above general formula.
Has from three components of O _2, Me _m O _n. Therefore, in order to produce the crystalline alkali metal silicate in the detergent composition, each component is required as a raw material,
In the present invention, known compounds are appropriately used without any particular limitation. For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used.
Specifically, for example, the raw material of the M ₂ O component is NaO
H, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO ₄
Etc. is, as a material of Me _m O _n component, CaCO _3, M
gCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO,
ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

The method for preparing the crystalline alkali metal silicate in the detergent composition is as follows: the above-mentioned raw material components are mixed in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline alkali metal silicate are obtained. 300 to 1500 ° C., preferably 500 to 1000 ° C., more preferably 600 to 90 ° C.
A method of firing at a temperature of 0 ° C. for crystallization is exemplified.
In this case, if the heating temperature is lower than 300 ° C., the crystallization is insufficient and the water resistance is poor. Heating time is usually 0.1 to 24
Time. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

Next, the crystalline alkali metal silicate having the above composition will be described. The crystalline alkali metal silicates have the general formula _{(2) M 2 O · x'SiO} 2 · y'H 2 O (2) ( wherein, M represents an alkali metal, x '= 1.5 to 2 .
6, y ′ = 0 to 20. ), Wherein x ′ and y ′ in the general formula (2) are 1.7 ≦ x ′ ≦ 2.
2, y ′ = 0 is preferred, and the cation exchange capacity is at least 100 CaCO ₃ mg / g or more, preferably 20
A substance having an ion-capturing ability in a detergent can be used in which 0 to 400 CaCO ₃ mg / g can be used.

The production method of such a crystalline alkali metal silicate is described in JP-A-60-227895. Generally, amorphous glassy sodium silicate is used in an amount of 200 to 200.
It is obtained by firing at 1000 ° C. to make it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7,
127-138 (1966), Z. Kristallogr., 129 , 396-404 (1969)
And so on. The crystalline alkali metal silicate is available from Hoechst under the trade name “Na-SKS-6” (δ
-Na ₂ Si ₂ O ₅ ) can be obtained in powder or granular form. In the case of a detergent for clothing, these crystalline silicates may be blended in base detergent particles, or may be dry-blended as separate particles.

Metal ions other than crystalline alkali metal silicates
The sequestering agent other than the alkali metal silicate in the detergent composition has a Ca ion capturing ability of 200 CaCO ₃ m.
Those having g / g or more are preferred. In particular, those containing 10% by weight or more of a carboxylate polymer are preferable, and specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the general formula (3). .

[0048]

Embedded image

(Wherein X ₁ is methyl, H or COOX
₃ , X ₂ represents methyl, H or OH, and X ₃ represents H, an alkali metal, an alkaline earth metal, NH ₄ or ethanolamine. )

In the general formula (3), examples of the alkali metal include Na, K, and Li, and examples of the alkaline earth metal include Ca and Mg.

The polymer or copolymer used in the detergent composition is, for example, acrylic acid, (anhydride) maleic acid,
It is synthesized by a polymerization reaction of methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid and salts thereof, a copolymerization reaction of each monomer, or a copolymerization reaction with another polymerizable monomer. Examples of other copolymer monomers used for copolymerization at this time include, for example, aconitic acid, itaconic acid, citraconic acid,
Fumaric acid, vinylphosphonic acid, sulfonated maleic acid,
Examples include diisobutylene, styrene, methyl vinyl ether, ethylene, propylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol if hydrolyzed after copolymerization), and acrylic esters, but are particularly limited. is not. The polymerization reaction is not particularly limited, and a generally known method can be used. Also, Japanese Patent Application Laid-Open No. 54-5219
No. 6, a polyacetal carboxylic acid polymer such as polyglyoxylic acid can also be used.

In the detergent composition, the above-mentioned polymer and copolymer are those having a weight average molecular weight of 800 to 1,000,000, preferably 5000 to 200,000.

The copolymerization ratio between the repeating unit of the general formula (3) and another copolymerizable monomer in the case of copolymerization is not particularly limited, but is preferably the repeating unit of the general formula (3) / other copolymerization. Monomer = copolymerization ratio in the range of 1/100 to 90/10. The above polymer or copolymer is preferably contained in the detergent composition in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, and still more preferably 5 to 15% by weight.

Further, an aluminosilicate having an ion exchange capacity represented by the following formula (4) of 200 CaCO ₃ mg / g or more can be used. _{x "(M 2 O) ·} Al 2 O 3 · y" (SiO 2) · w "(H 2 O) (4) ( wherein, M represents alkali metals such as sodium and potassium,
x ″, y ″, w ″ represent the number of moles of each component, and generally 0.7 ≦ x ″ ≦ 1.5, 0.8 ≦ y ″ ≦ 6, w ″
20. )

Examples of the above aluminosilicate include crystalline ones and amorphous ones. As the crystalline ones, those represented by the following general formula are particularly preferable. _{Na 2 O · Al 2 O 3} · ySiO 2 · wH 2 O ( wherein, y is 1.8 to 3.0, w represents a number of 1-6.) As the crystalline aluminosilicate (zeolite) , Type A,
Average primary particle size 0.1 represented by X-type and P-type zeolites
Synthetic zeolites of 〜１０10 μm are preferably used. The zeolite may be used as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry or the slurry.

The above-mentioned crystalline aluminosilicate can be produced by a conventional method. For example, JP-A-50-123
81 and JP-A-51-12805 can be used.

On the other hand, an amorphous aluminosilicate represented by the same general formula as that of the above-mentioned crystalline aluminosilicate can be produced by a conventional method. For example, SiO ₂ and M ₂ O
(M means an alkali metal) molar ratio of SiO ₂ /
An M ₂ O = 1.0~4.0, the molar ratio of between H ₂ O and M ₂ O is using alkali metal silicate solution is a _{H 2 O / M 2 O =} 12~200, M to The molar ratio of ₂ O to Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0;
The molar ratio of ₂ O to M ₂ O is H ₂ O / M ₂ O = 6.0 to 50
The aqueous solution of a low alkali alkali metal aluminate, which is 0, is usually added under a strong stirring at a temperature of 15 to 60 ° C, preferably 30 to 50 ° C.

Next, the resulting white precipitate slurry is heated at a temperature of usually 70 to 100 ° C., preferably 90 to 100 ° C.
It can be advantageously obtained by performing a heat treatment usually for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. At this time, the addition method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate. According to this method, the ion exchange capacity is 100 CaCO ₃ mg / g or more, and the oil absorption capacity is 80 m.
An amorphous aluminosilicate oil-absorbing carrier of 1/100 g or more can be easily obtained (see JP-A-62-191417 and JP-A-62-191419). Other sequestering agents include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and salts thereof, -Phosphonobutane-1,2-
Examples include salts of phosphonocarboxylic acids such as dicarboxylic acids, salts of amino acids such as aspartic acid and glutamic acid, and aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate.

Other Ingredients Other ingredients in the detergent composition include, as alkaline agents, crystalline and amorphous alkali metal silicates, alkali metal salts such as carbonates and sulfites, and organic compounds such as alkanolamines. Various substances such as amines are exemplified. In addition, polyethylene glycol, polyvinyl alcohol, non-dissociating polymers such as polyvinylpyrrolidone, diglycolic acid, builders such as salts of organic acids such as oxycarboxylates, and carboxymethylcellulose are known to be generally incorporated into detergents. Anti-fading agents, anti-staining agents and the like.

Builders such as non-dissociated polymers and salts of organic acids;
Anti-fading agent, anti-staining agent, anti-caking agent, antioxidant, bleach, bleach activator, fluorescent dye, bluing agent,
Flavors and the like can be included, and the like. As the bleaching agent, sodium percarbonate and sodium perborate are preferable, and when it is used as a bleaching detergent, 1 to 95%, particularly 20 to 95% is blended.

In addition, the following components can be contained in the detergent composition. That is, a lower alkylbenzene sulfonate having about 1 to 4 carbon atoms, a sulfosuccinate,
Anti-caking agents such as talc and calcium silicate,
Tertiary butyl hydroxytoluene, an antioxidant such as distyrenated cresol, a bleaching agent such as sodium percarbonate or a bleaching activator such as tetraacetylethylenediamine, a fluorescent dye, a bluing agent, a fragrance, etc. These are not particularly limited, and may be mixed according to the purpose.

[0062]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 9 and Comparative Examples 1 and 2 An extruded product was obtained by mixing and extrusion. Details are described below. a) Premixing Step As a pretreatment for extrusion molding, mixing of the enzyme-containing granulated components and heating to a predetermined temperature (the melting point of the binder) were performed. Specifically, 30 kg of the enzyme-containing granulating component was charged into a Nauta mixer manufactured by Hosokawa Micron Corporation, and the jacket temperature was set at 7 ° C.
Mixing / heating was performed at 0 ° C. to a powder temperature of 60 ° C. Tables 1 and 2 show the compositions. In Examples 1 to 5 and Comparative Example 1, CFD raw powder / PEG / crushed anhydrous sodium sulfate = 20 / X /
Balance (% by weight), in Example 6, CFD bulk powder /
PEG / pulverized anhydrous sodium sulfate = 10 / X / balance (% by weight). In Example 7, CFD raw powder / nonion / pulverized anhydrous sodium sulfate = 20 / X / balance (% by weight), Example 8,
9 and Comparative Example 2, KAP bulk powder / PEG / ground anhydrous sodium sulfate = 50 / X / balance (% by weight).

As the raw enzyme powder, CFD: WO94 / 2
A cellulase-containing bulk powder obtained by the method described in No. 6881 and a protease-containing bulk powder obtained from a high titer strain of KAP: Bacillus KSM-K16 (International Deposit No. BP3376) were used. As the thermoplastic water-soluble binder, PEG: polyethylene glycol manufactured by Kao: PEG
6000 (melting point: about 58 ° C.), and nonion: Kao's polyoxyethylene stearyl ether: Emulgen 320
0 (melting point about 45 ° C.) was used. The amount of water in the enzyme-containing granulated component was determined by measuring the amount of water released while maintaining the temperature in a 105 ° C. atmosphere for 60 minutes.

B) Extrusion Molding Step The mixture was supplied to an extrusion granulator (Peletter Double EXD-60, manufactured by Fuji Paudal Co., Ltd.), and the mixture was extruded and compacted through a screen having a predetermined diameter. The obtained extrudate was cooled with a vibration cooler (Fuji Paudal Co., Ltd .: Vibro / flow dryer VDF / 6000 type).

The evaluation of the molded state of the obtained extruded product was as follows:
Visual inspection of the extruded product and the vibration-cooled product were performed by visual observation. The extruded product was in the shape of a cylindrical noodle and was not united with each other. The extruded product was united with each other and united after vibration cooling. The as-prepared product is in a lump, the product immediately after extrusion is united, but the one that returns to the noodle by vibration cooling is sticky ant, the extruded product is not cylindrical, the molding is poor, and the extruded product is not formed by shattering The product was made unmoldable.
The actual load / capacity indicates the power required to obtain an extrudate having a unit weight, and is an index indicating the lubricity of the mixture. It depends on the extruder used, the specific heat of the mixture, etc.
In this embodiment, it is preferably 0.035 (A / (kg / hr)) or less.

The screen temperature is the temperature at which the molded product passes through the screen, and is 95 ° C. from the viewpoint of suppressing the inactivation of the enzyme.
Or less, more preferably 80 ° C. or less. The residual activity before storage was calculated as follows. Residual activity (%) before storage = [C ₁ / (Cp × Y)] × 10
0 Here, C ₁ : enzymatic activity of the extruded product Cp: activity of the original enzyme powder Y: the weight of the original enzyme powder in the extruded product, where 1 is the extruded product. Further, the 90% dissolution time of the obtained molded article was also examined. As a specific measuring method, a method described later was used.

[0067]

[Table 1]

[0068]

[Table 2]

Examples 10 to 17 The extruded products obtained in the above Examples were subjected to a crushing treatment, a sphering treatment and a coating treatment to obtain enzyme granules. c) Crushing / Spheronizing process-When using a speed mill A 2 kg extruded product is cooled to about room temperature, and then crushed by a pulverizer (Fuji Paudal Co., Ltd .: Speedmill FL).
-200 type). -When using a marmellaizer A 2 kg extruded product is cooled to about room temperature, and treated with a sphering machine (manufactured by Fuji Paudal Co., Ltd .: Marumeraizer Q-400) at 500 rpm for 10 minutes. Then, a sphering treatment was performed.

At the time of using the granulation king 24 kg of the extruded product was put into a stirring rolling granulator (Mitsui Mining Co., Ltd./Granno TM50B), and the upper blade stirring blade rotation speed 1500 rpm, the lower blade stirring blade rotation speed 60r
Disintegration treatment was performed at pm for 10 minutes. Subsequently, hot water of 60 ° C. was flowed through the jacket, and the upper blade stirring blades were rotated at 100 rpm.
The spheroidizing treatment was performed at 0 rpm for 10 minutes at a lower blade stirring blade rotation speed of 30 rpm.・ When using a high-speed mixer, a 5 kg extruded product is agitated with a rolling granulator (Fukae Industry Co., Ltd.)
/ High speed mixer, FS-10 type)
Main shaft rotation speed 240 rpm, crushing blade rotation speed 2700 rpm
m for 20 minutes. However, in the granulation and high-speed mixers, some spheroidization progressed in the crushing process.

D) Coating step-At the time of using the granule king 12 kg of the spheroidized material and 12 kg of the coating raw material were stirred by a hot rolling water of 60 ° C. in a jacket (Mitsui Mining Co., Ltd.)
Production / Granulation TM50B), and the mixture was subjected to stirring granulation for 20 minutes at an upper blade stirring blade rotation speed of 1000 rpm and a lower blade stirring blade rotation speed of 30 rpm to coat a spherical product. -When using a high speed mixer 5 kg of the crushed material and 1.67 kg of the coating material are stirred and rolled with a hot water of 60 ° C in a jacket. (Fukae Kogyo Co., Ltd./High Speed Mixer, Model FS-10) , The spindle speed 240 rpm, the crushing blade speed 270
The mixture was stirred and granulated at 0 rpm for 100 minutes to coat the crushed product. Further, 3.33 kg of coating material was added, and the mixture was further stirred and granulated for 10 minutes under the same conditions. Each of the coating materials is a mixture of talc / titanium oxide / PEG / cyanine blue = 78/12/10 // 0.2 (parts by weight).

Comparative Examples 3 and 4 (Nucleation-Free Agitation Granulation) As a dry granulation method without using an extruded product as an extrusion core,
Enzyme granules were produced by a nucleation-free stirring tumbling granulation method. That is, using the same high-speed mixer as in the example, 5 kg of a coreless tumbling granulated raw material (CFD raw powder / PEG / crushed anhydrous sodium sulfate / titanium oxide = 18/13/65/4 (% by weight)) was charged, and the main spindle was prepared. Rotation speed 250 rpm, crushing blade rotation speed 300
Stirring was performed for 2 minutes in a jacket at 0 rpm and 30 ° C., and then hot water at 70 ° C. was flowed through the jacket, followed by stirring and rolling for 32 minutes (Comparative Example 3). 1.4 kg of the same coating material as in the example was added to 4.2 kg of the obtained agitated rolling particles.
Is added, the main shaft rotation speed is 240 rpm, and the crushing blade rotation speed is 2
The mixture was stirred and granulated at 700 rpm in a jacket at 60 ° C. for 100 minutes, and 2.8 kg of a coating material was added. The mixture was further stirred and granulated for 10 minutes under the same conditions to coat the particles (Comparative Example 4).

The enzyme granules obtained in Examples 10 to 17 and Comparative Examples 3 and 4 were evaluated. 1410 μm
"On" is the amount of the granules remaining on the sieve obtained by sifting the obtained enzyme granules through a sieve having a sieve of 1410 μm and expressed as a percentage by weight in the total enzyme granules. is there. 350
The μm pass is a value expressed by weight% of the total enzyme granulated product when the obtained enzyme granulated product is passed through a sieve having a sieve of 350 μm sieve and passed through the sieve. It is. It also passed through a 1410 μm sieve with a sieve opening,
The value of the amount of enzyme granules (that is, particles having a particle size of 350 to 1410 μm) remaining on the sieve having a sieve opening of 0 μm and expressed in% by weight of the total enzyme granules is shown in the table. It is shown in the item of "Product". As the average particle size of the enzyme granulated product, a value of 50% particle size was used based on a particle size distribution according to a dry sieving method described in Japanese Industrial Standard JIS-K0069 (1192).

The sphericity was measured by using an image analyzer to measure the extrudate before coating (Examples 10 to 13 and 16), agitated rolling particles (Comparative Example 3), and particles after coating (Example 14). ,
15, 17 and Comparative Example 4) are projection figures, and are values calculated from the longest width (L) and area (A) using the following formula. Sphericity = (L ² / A) × (π / 4) × 100 (%)

Solubility (90% dissolution time) Put 1 liter of water at 10 ° C. into a 1 L beaker, and add
5 g of an enzyme granulated product having a particle size of 350 to 1410 μm is placed in a stirrer piece having a size of m and the time required for the electric conductivity of the solution to reach 90% of the equilibrium value is dissolved by 90%. Time. The thickness of the coating layer was measured by enlarging the cross section of the granulated product with an optical microscope and measuring N = 50.
The average value at 0 was used.

Storage stability (remaining activity after storage ) The storage stability of the enzyme granules in a detergent containing no bleach and a detergent containing a bleach was examined.
High bulk density detergent A (no bleach) and high bulk density detergent B
(With bleach) 50 g of enzyme granules for 5 g each
mg was added and mixed to prepare a detergent composition. The obtained detergent composition was stored at 30 ° C. and 80% RH for 4 weeks. Thereafter, enzyme granules were picked up from the detergent composition and the activity was measured (C ₂ ). And the residual activity after storage was calculated as follows. Residual activity (%) after storage = [C ₂ / (Cp × Y)] × 10
0 Here, C ₂ : the enzyme activity of the enzyme granulated product Cp: the activity of the enzyme powder Y: the weight of the enzyme powder in the extruded product when the extruded product is defined as 1. In addition, as the enzyme granulated product, a sieved product having a size of 350 to 1410 μm was used.

[0077]

[Table 3]

[0078]

[Table 4]

The above high bulk density detergent was prepared as follows. (1) Preparation of spray-dried particles The components shown in Table 5 were mixed with water to prepare a detergent slurry having a solid content of 50% by weight. The slurry was spray-dried at about 65 ° C. using a countercurrent spray-drying apparatus to obtain spray-dried particles.
The volatile content (loss at 105 ° C. for 2 hours) of the obtained spray-dried particles was 4% by weight.

[0080]

[Table 5]

The components in the above table will be described below. _{LAS-Na (C 10 ~C 13} ): straight-chain alkyl (C ₁₀ -C
₁₃₎ sodium benzenesulfonate _{AS-Na (C 12 ~C 16} ): alkyl (C ₁₂ -C ₁₆₎ sodium sulfate nonionic surfactant: carbon atoms polyoxyethylene alkyl ethers [alkyl chains 12-14 (mean 12 .8)
Average 8 ethylene oxide in primary saturated alcohol
AA / MA copolymer: sodium salt of acrylic acid / maleic acid copolymer (sokalan CP-5) Tinopearl CBS-X: fluorescent dye, distyrylbiphenyl derivative (manufactured by Ciba Geigy) Whitetex SA: fluorescence Dye, bis- (triazinylamino) -stilbene-disulfonic acid derivative (Sumitomo Chemical Co., Ltd.)

(2) Preparation of high bulk density detergent A (no bleach) 78 parts by weight of spray-dried particles obtained from the detergent slurry A in Table 5 above and a crystalline aluminosilicate powder (4A zeolite powder) And 3 parts by weight of an average particle size of 2.7 μm (manufactured by Tosoh Corporation), and the mixture was charged into a high-speed mixer to crush the spray-dried particles and perform stirring granulation. At that time, 4 parts by weight of a nonionic surfactant (polyoxyethylene alkyl ether obtained by adding an average of 6 moles of ethylene oxide to a primary saturated alcohol having an alkyl group carbon number of 12 and a water content of 10% by weight) is added by spraying. The processing was performed while. Thirty seconds before the end of granulation, 9 parts by weight of the same powder zeolite as that mixed with the spray-dried particles was added, and the mixture was stirred again. Next, the granulated product was sieved with a sieve having a mesh size of 1.3 mm. The final sieved product was mixed with 5 parts by weight of a crystalline silicate [SKS-6 (granule), Hoechst Tokuyama Co., Ltd.] using a V blender to obtain a final granular detergent.

(3) Preparation of high bulk density detergent B (with bleaching agent) Nonionic surfactant (polyoxyethylene alkyl ether obtained by adding an average of 6 moles of ethylene oxide to a primary saturated alcohol having 12 alkyl groups of carbon atoms) , Water content 10% by weight), 5 parts by weight, crystalline aluminosilicate powder (4A type zeolite powder, average particle size 2.7 μm, Tosoh Corporation)
16 parts by weight), and 1 part by weight of a sodium salt of an acrylic acid / maleic acid copolymer, and 51 parts by weight of spray-dried particles obtained from the B detergent slurry in the above table are mixed in advance. LAS-N with a solid content of 50% by weight
The mixture was put into a batch mixer together with 8 parts by weight of the slurry a and preliminarily mixed, and further kneaded by a twin-screw kneader.
The paste obtained by this kneading is mixed with 50 to 200 ba
r, extruded and granulated by a string-shaped extruder so as to have a diameter of 1 to 1.2 mm and a length of 1 mm, and subjected to a spheroidizing treatment with a marmellaizer. At that time, 3 parts by weight of a conventionally used powder zeolite was added to coat the surface. Next, after drying and cooling were performed by a fluidized-bed drying device (blast temperature of 75 to 80 ° C.), the resultant was sieved with a 1.3 mm mesh sieve. The sodium percarbonate (50
0 μm) and 15 parts by weight of TAED (tetraacetylethylenediamine) were mixed with a V blender to obtain a final granular detergent.

From the above examples and comparative examples, the following has been found. The molded product extruded by the method of the present invention is
Since the residual activities before storage are all high values, it has been found that the production method of the present invention is an excellent method that can suppress the inactivation of the enzyme due to heat generation, even though it is performed in a non-aqueous system. (Examples 1 to 9). On the other hand, when the amount of the thermoplastic binder is out of the predetermined range, a molded product cannot be obtained (Comparative Example 1), and extrudates are united and a noodle-shaped molded product cannot be obtained (Comparative Example 2). Met.

Further, from Examples 10 to 17, it can be seen from the results that the storage stability of the enzyme granulated product is improved by applying the coating. In particular, the higher the degree of spheroidization of the extruded product, the greater the effect of improving the storage stability. I understood. On the other hand, from the viewpoint of low-temperature solubility, it is preferable that no coating is applied. Therefore, it is necessary to adjust the coating thickness of the enzyme granules according to the blending environment of the enzyme granules, use conditions, and the like. In addition, by applying a coating,
It can be seen that high storage stability is exhibited even in the presence of a bleaching agent. On the other hand, from Comparative Examples 3 and 4, it can be seen that the storage stability is inferior to that of the granulated product according to the present invention due to the widened particle size distribution of the granulated product, the increase in surface area and the uneven thickness of the coating layer.

As shown in FIG. 1, the agitated tumbling granulated product using the extruded product as an extruded core has a very sharp particle size distribution, a uniform coating thickness and a good storage stability, as shown in FIG. It has the advantage of being expensive and hard to classify with other components when blended in a detergent or the like. On the other hand, since the coating thickness of the non-nucleated agitated tumbling granules differs depending on the particle size,
Not only is the storage stability low, but the problem that the enzyme activity value differs for each particle size has arisen (particle size 1410 to 1000 μm).
m product activity / 500-710 μm product activity = about 1.5
Times). In the present invention, this effect is small because the particle size distribution is sharp. In addition, since granulation using extrusion can easily control the product particle size by adjusting the screen diameter during extrusion molding, it is easy to produce granules having a size suitable for the particle size of the compounded product. I got it. In addition, because of the nucleation, the advantage of little adhesion inside the machine was also recognized.

[0087]

Industrial Applicability The method for producing an enzyme granule of the present invention provides a method for producing an enzyme granule in which a decrease in enzyme activity is suppressed. Furthermore, the enzyme granules obtained by the method of the present invention have a narrow particle size distribution, so that they are difficult to classify even when incorporated in a detergent or the like. Furthermore, the production method of the present invention has a high degree of freedom in composition, and furthermore, there is little adhesion of raw materials and the like to a machine used for production.

[Brief description of the drawings]

FIG. 1 shows Examples 14, 15, and 17 and Comparative Example 4.
It is a figure which shows the particle size distribution of the enzyme granulated product obtained in FIG. In the figure, Δ indicates data of Example 14, ▲ indicates data of Example 15, ○ indicates data of Example 17, and ● indicates data of Comparative Example 4.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shitsu Shikata 1334 Minato, Wakayama City, Kao Corporation Research Institute (72) Inventor Masashi Nomura 1334 Minato, Wakayama City, Kao Corporation Research Center

Claims (10)

[Claims] 1. Step a: a melting point or a softening point of 35 to 8
Mixing a substantially water-free enzyme-containing granulating component containing 10 to 40% by weight of a thermoplastic water-soluble binder at 0 ° C., step b: mixing the mixture obtained in step a with the thermoplastic water-soluble Extruding at a temperature equal to or higher than the melting point or softening point of the binder. 2. The method according to claim 1, wherein the thermoplastic water-soluble binder is at least one substance selected from the group consisting of polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene phenol ether. Method. 3. The method according to claim 1, further comprising the step of: c) cooling the extruded product obtained in the step b. 4. The production method according to claim 1, further comprising the step of: d) a step of spheroidizing the extruded product obtained in the step b or c. 5. The method according to claim 4, wherein the sphericity of the extruded product has an average sphericity of 100 to 200%. 6. The method according to claim 1, further comprising a step e: a step of coating the extruded product or the spheroidized extruded product obtained in the step b, the step c, or the step d. Production method. 7. The production method according to claim 6, wherein the extruded product or the spheroidized extruded product is coated by agitating and rolling granulation. 8. The method according to claim 6, wherein the thickness of the coating layer is 200 μm or less. 9. The composition of the coating layer is such that the poorly water-soluble powder is 20 to 20.
5% to 30% by weight of a thermoplastic water-soluble binder having a melting point or a softening point of 35 to 80 ° C.
8. The production method according to any one of the above items 8. 10. A detergent composition comprising a mixture of an enzyme granulated product obtained by the production method according to claim 1 and a detergent.