JP2909888B2 - Enzyme-containing granules, method for producing the same, and detergent and bleach compositions containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an enzyme-containing granule useful as a component of a detergent, and more particularly, to an enzyme-containing granule having excellent enzyme stability, no dusting property, and good productivity. The present invention relates to a granulated product, a method for producing the same, and a detergent and bleaching composition containing the same.

[0002]

2. Description of the Related Art In addition to detergents and bleaching agents, various enzymes are often added to detergents and bleaching agents for clothing in order to enhance the washing action. These enzymes are usually granulated and compounded so that they do not deactivate during storage and exhibit sufficient activity during the washing step.

[0003] It is known that the enzyme-containing granules decrease the stability of the enzyme when a bleaching agent, a surfactant, a builder for washing, etc. are mixed, and the enzyme activity is remarkably reduced when a bleaching agent is added. I have. In addition, the granulated material for the cleaning agent, in consideration of the decrease in productivity due to classification, etc., it is necessary to control the particle size and the bulk specific gravity to some extent, but the particle size distribution is particularly narrow, and the productivity is high. Granules are desired. Further, since it is necessary for workers and consumers at the time of production to avoid direct contact with the enzyme, granules having no dusting property are desired.

In response to these problems, the present inventors have found that an enzyme granulated product having a narrow particle size distribution can be obtained with high productivity by using a stirring tumbling granulator. Filed (JP-A-62-257990).

[0005]

However, the granulated product obtained by the tumbling granulation has not yet been sufficiently satisfactory in terms of the storage stability of the enzyme, dust generation, and the like.
Accordingly, an object of the present invention is to provide an enzyme-containing granule having no dusting property, good storage stability of an enzyme, and good productivity, a method for producing the same, and a detergent and bleaching composition containing the same. To provide.

[0006]

The present inventors have conducted intensive studies on the storage stability and dusting properties of the enzyme and the composition of the granulated product. The present invention has been found that if two or more types of water-insoluble or hardly soluble inorganic particles having different particle diameters are coated in combination with a binder, a granulated product having almost no dusting property and extremely excellent storage stability can be obtained. Was completed.

[0007] That is, the present invention relates to a method of preparing an enzyme-containing powder in the following manner: (a) water-insoluble or poorly soluble inorganic particles having an average particle size of 1 to 100 µm; It is intended to provide an enzyme-containing granulated product, wherein a coating layer containing insoluble or hardly soluble inorganic particles and a binder (c) is formed.

[0008] Further, the present invention relates to a granular material containing an enzyme,
(A) forming a coating layer containing water-insoluble or hardly soluble inorganic particles having an average particle size of 1 to 100 μm, (b) water-insoluble or hardly soluble inorganic particles having an average particle size of 0.01 to 0.8 μm, and (c) a binder; And a method for producing an enzyme-containing granulated product.

Further, the present invention provides a method for preparing an enzyme-containing powder containing (a) water-insoluble or poorly soluble inorganic particles having an average particle size of 1 to 100 μm, and (b) water having an average particle size of 0.01 to 0.8 μm. It is intended to provide an enzyme-containing granulated material characterized in that a coating layer containing insoluble or hardly soluble inorganic particles and a binder (c) is formed, and a detergent composition containing a surfactant.

Furthermore, the present invention relates to a method of preparing an enzyme-containing powder having the following features: (a) water-insoluble or poorly soluble inorganic particles having an average particle size of 1 to 100 μm; It is intended to provide an enzyme-containing granulated product characterized in that a coating layer containing water-insoluble or poorly soluble inorganic particles and a binder (c) is formed, and a bleaching agent-containing bleaching agent composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The granulated product of the present invention is, as described above,
A granule containing an enzyme is used as a nucleus.
The layer containing (b) and (c) is coated.

The granules containing the enzyme which is the core in the granulated product of the present invention include (1) a granule of the enzyme alone, (2) the enzyme and water-soluble substance particles having a particle size of 0.2 to 1.2 mm. (3) Enzyme, powder and granules containing water-soluble substance particles having a particle size of 0.2 to 1.2 mm and a binder, (4) Enzyme, particle size of 0.
2 to 1.2 mm water-soluble substance particles, binder and powder containing (a), (5) enzyme, powder containing water-soluble substance, binder and (b), (6) enzyme, particle size 0.2
Water-soluble substance particles of up to 1.2 mm, binder, (a)
And (b).

[0013] The enzyme used in the present invention is not particularly limited, and examples thereof include enzymes mixed with detergents, such as one selected from proteases, esterases and carbohydrases, and mixtures thereof.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, papain,
Examples include aminopeptidase and carboxypeptidase.

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

As carbohydrase, cellulase,
Examples include maltase, saccharase, amylase, pectinase, α- and β-glycosidase.

[0017] For detergents or bleaching agents, enzymes produced by microorganisms obtained by culturing are advantageous in price. Usually, it is preferable to use a dried powdery enzyme produced by such a microorganism after culturing and separating. The average particle size is desirably 20% or less of the average particle size of the water-soluble substance particles. At the time of powdering, an enzyme stabilizer such as calcium chloride and a powdering aid such as sodium sulfate and sodium chloride may be blended.

The water-soluble substance particles having an average particle diameter of 0.2 to 1.2 mm are particles that act as a core substance in the step of producing a granular material containing an enzyme, such as sodium chloride, potassium chloride, sodium sulfate and sodium carbonate. And sugar, but sodium chloride is particularly preferred.

In the present invention, the average particle size and the particle size distribution (by volume) are measured by a laser diffraction type particle size distribution measuring device S.
It measured using ALD-1100 type (made by Shimadzu Corporation).

It is desirable that the particle size distribution of the water-soluble substance particles is narrower, and it is particularly preferable to remove coarse particles having a size twice or more the average particle size. The water-soluble substance particles preferably have a melting point or softening point of 80 ° C. or higher, and more preferably those having low hygroscopicity, high mechanical strength and low adhesiveness.

Examples of the type of the water-insoluble or hardly soluble inorganic particles having an average particle size of 1 to 100 μm of the component (a) include talc, titanium oxide, calcium carbonate, zeolite, magnesium carbonate, activated clay, kaolin and the like. Of these, talc, calcium carbonate, zeolite, magnesium carbonate, activated clay, and kaolin are preferable, and two or more kinds may be used in combination as long as the average particle diameter is within this range. A more preferred average particle size is in the range of 2 to 80 μm, and a particularly preferred average particle size is 2 to 60 μm.

Average particle size of component (b): 0.01 to 0.8 μm
Examples of the type of the water-insoluble or hardly soluble inorganic particles of m include the same as those listed as the component (a). Among them, titanium oxide is particularly preferable, and as long as the average particle diameter is within this range, 2 is preferable. Mixtures of more than one species may be used.
A more preferred average particle size is 0.1 to 0.8 μm, and a particularly preferred average particle size is 0.1 to 0.6 μm.

In the present invention, two kinds of water-insoluble or hardly soluble inorganic particle components (a) having different average particle sizes are provided in the coating layer.
The combination of the component (b) and the component (b) has the greatest feature. By using the component (a) and the component (b) together, a strong coating layer with low dusting property is formed on the granulated material, The storage stability of the enzyme in the granulated product is improved.

The binder used in the present invention is preferably a water-soluble organic compound having a melting point or softening point of 35 to 70 ° C. Specific examples of the binder include polyethylene glycol, polyoxyethylene-polyoxypropylene glycol, non-ionic surfactants such as polyoxyethylene alkyl ether,
One or a mixture thereof can be used.

Further, in order to stabilize the enzyme, various inorganic salts such as calcium salts and magnesium salts, or organic substances such as surfactants, sugars and carboxymethyl cellulose are used in the granulated product of the present invention. Is also possible. Furthermore, synthetic hectorite or sepiolite can be blended to adsorb odorous components derived from culture. It is also optional to add a dye or a dye to color the enzyme granules. These components may be added in advance in the production process of the enzyme powder, or may be added in the production process of the enzyme-containing powder,
Alternatively, it may be added in the coating step of the present invention.

In the granulated product of the present invention, the weight ratio between the enzyme-containing powder and the coating layer is not particularly limited.
0.1 to 1: 0.7, preferably 1: 0.2 to 1: 0.6, and the weight ratio of component (a): component (b) is 1: 0.1
１1: 1, more preferably 1: 0.1 to 1: 0.5.
The weight ratio of [the sum of the component (a) and the component (b)]: [component (c)] is preferably 1: 0.05 to 1: 1, more preferably 1: 0.08 to 1: 0.3. .

When the water-soluble substance particles are contained in the enzyme-containing powder, the amount of each component is not particularly limited, but the amount of the enzyme is 10 to 100 parts by weight per 100 parts by weight of the water-soluble substance particles. Parts by weight, component (a) is 40 to 120 parts by weight, component (b) is 10 to 50 parts by weight, and component (c) is 10 parts by weight.
Preferably, it is 〜60 parts by weight.

The enzyme-containing granule of the present invention is prepared by first preparing an enzyme-containing powder having the above-mentioned constitutions (1) to (5), and adding the components (a), (b) and (c) thereto. Manufactured by coating.

In the present invention, both the preparation of the enzyme-containing powder and the coating are preferably carried out by a dry granulation method, and the coating is more preferably carried out by a tumbling granulation method. It is particularly preferred to carry out the tumbling granulation method.

Specific examples of the agitating tumbling granulator include Henschel mixer (Mitsui Miike Kakoki Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator (Fuji Sangyo Co., Ltd.) and the like. Can be mentioned. The common feature is that they have a vertical stirring shaft with stirring blades mounted inside a rigid mixing tank. Ladyge Mixer (Ladyge), a model granulator with a horizontal stirring shaft
Can also be used as well.

The case where both preparation and coating of the enzyme-containing powder are carried out by agitating tumbling granulation will be described as an example. Enzymes, water-soluble substance particles,
The binder and other components are charged, and the mixture is gently stirred and mixed while flowing a heating medium such as warm water into the jacket of the granulator. Attention must be paid to vigorous mixing at this point, since the destruction of the water-soluble substance particles occurs. Eventually, when the temperature of the raw material in the tank exceeds the melting point or the softening point of the binder, granulation starts, centering on the water-soluble substance particles, but spherical particles are formed due to the rolling operation on the surface of the stirring blade. Is done. If the stirring is further continued, coarse agglomeration due to agglomeration of the particles may be generated, and the thermal effect of the enzyme may be increased, which is not preferable.However, detecting the optimal end point of the granulation is generally performed. Utilizing that the power required for stirring (for example, current value) increases when granulation starts,
It can be easily carried out by trially conducting the intended composition of the granulated product and using a stirring tumbling granulator in advance. After obtaining the primary granules (enzyme-containing granules) in this way, the components (a), (b), (c) and other components are further charged and the same operation may be performed. .

The thus obtained enzyme granules can be coated with polyethylene glycol or a nonionic surfactant as required.

To prepare a detergent or bleaching composition using the enzyme-containing granules obtained as described above, various surfactants, bleaching agents, inorganic electrolytes, chelating agents are added to the granules. And the like, and may be produced by a conventional method.

The amount of the enzyme-containing granules to be added to the detergent composition or the bleaching composition varies depending on the specific activity in the enzyme powder, the type of the enzyme, and the content of the enzyme in the granules. 0
It is preferably from 01 to 70% by weight, particularly preferably from 0.1 to 10% by weight.

As the surfactant, alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated surfactant as anionic surfactant 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 acidic phosphate, alkyl or alkenyl phosphate or salt thereof But; amphoteric surfactants such as carboxy or sulfobetaine type surfactants; nonionic surfactants such as polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether,
Higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, fatty acid glycerin monoesters, alkylamine oxides, alkyl glycosides and the like; and cationic surfactants such as quaternary ammonium salts. These surfactants are present in the cleaning composition of the present invention in an amount of from 10 to 90% by weight, especially from 1 to 90% by weight.
It is preferable to mix 0 to 50% by weight. The bleaching agent of the present invention preferably contains 0.5 to 10% by weight, particularly 1 to 5% by weight.

Examples of the inorganic electrolyte include an alkali agent such as carbonate, bicarbonate, silicate, borate and alkanolamine, and sulfate. This electrolyte is usually 0
It is blended in an amount of from 90 to 90% by weight, and more preferably from 1 to 40% by weight.

Examples of the chelating agent include phosphates such as tripolyphosphate, pyrophosphate, and orthophosphate, and ethane-phosphate.
Salts of phosphonic acids such as 1,1-diphosphonate, salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, salts of amino acids such as aspartic acid and glutamic acid, nitrilotriacetic acid salts, ethylenediamine tetraethylene salt Polymer chelating agents such as aminopolyacetates such as acetate, polyacrylic acid and polyaconitic acid; salts of organic acids such as oxalic acid and citric acid; aluminosilicates; and the chelating agent is a detergent composition. Alternatively, it is usually blended in a bleach composition at 0 to 50% by weight, but more preferably at 1 to 20% by weight.

Examples of the bleaching agent include sodium percarbonate, sodium perborate, sodium hypochlorite, dichloroisosialic acid, and the like.
８５85% by weight, but 1-2% in the detergent composition.
0% by weight, and more preferably 60 to 85% by weight in the bleach composition.

Other minor components include a re-staining agent such as polyethylene glycol and carboxymethyl cellulose, an enzyme deactivating agent such as sulfite, a fluorescent dye, a bluing agent, a pigment, a caking inhibitor, a solubilizing agent, an enzyme Alternatively, an activator of a bleaching agent, a metal corrosion inhibitor and the like can be added as required.

The cleaning composition or the bleaching composition of the present invention is obtained by mixing the above-mentioned components in a conventional manner, and adding
It can be used as a detergent or bleach for tableware, dwelling, etc.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Enzyme-containing granules A were obtained from a raw material having the following composition using a high-speed mixer (FS-5, Fukae Kogyo Co., Ltd.).

[0043]

Composition: Salt (average particle diameter: 610 μm, particles having a particle size of 500 μm or less are 72.0 (weight%) 11%, particles having a particle size of 700 μm or more are 9%) Polyethylene glycol 6000 (Kao Corporation) 4.0 Enzyme powder (WO94 / 26881) ^{* 1} 18.5 Titanium oxide (average particle size 0.27 μm) 5.5

* 1: Enzyme powder (WO94 / 26881) Glauber's salt was added to an aqueous solution of alkaline α-amylase cultured and collected from a bacterium belonging to the genus Bacillus belonging to the genus Bacillus, Microorganism Deposit No. 10886. A powder having an average particle diameter of 20 μm obtained by drying with a cocurrent spray dryer was used. The amount of sodium sulfate is 48% based on the dried product.

All of the above-mentioned raw materials (total of 2 kg) were charged, and the agitator 360
The contents were stirred and mixed at a rpm of 900 rpm and a chopper at 900 rpm. A primary granule containing the enzyme was obtained by a granulation operation for about 15 minutes from the charging of the raw materials.

To the obtained primary granulated product, talc (average particle size: 36 μm) as component (a), titanium oxide (average particle size: 0.27 μm) as component (b) and polyethylene glycol 6000 as binder (c) Was added at the same time, and granulation was further performed for about 10 minutes to obtain enzyme granulated product A. The recovery rate of the granulated material A is 98% for 350 μm or more and 1000 μm or less.
It was obtained in the above high yield.

For comparison, two kinds of particles having different particle diameters were similarly granulated using titanium oxide (average particle diameter 0.27 μm) and water-soluble sodium sulfate (average particle diameter 16 μm). Enzyme granules B were obtained. 0.1 g of the obtained enzyme granule A or B is used as a percarbonate 10 as a bleaching agent.
g, and stored under the conditions of 40 ° C. and a relative humidity of 80%, and the storage stability was examined. Table 2 shows the results.

[0048]

[Table 2]

Table 2 shows that the enzyme-containing granules of the present invention containing the components (a) and (b) have extremely excellent storage stability. Further, the granulated product of the present invention hardly recognized dust generation.

Example 2 Alkaline cellulase (JP-A-57-1) was used as an enzyme powder.
No. 45199) was used. That is, calcium chloride and sodium sulfate are added to an aqueous solution of alkaline cellulase cultured and collected from a bacterium belonging to the genus Bacillus of Microorganism Deposit No. 1138, and dried by a cocurrent spray dryer. The powder having an average particle diameter of 50 μm obtained by the above method was used. The amount of calcium chloride and sodium sulfate is 0.5
% And 48%. Using the enzyme powder thus obtained, a primary granulated product was prepared in the same manner as in Example 1. Titanium oxide (average particle size 0.27 μm) was added to the obtained primary granules.
And talc (average particle diameter 36 μm), zeolite (average particle diameter 5.2 μm), kaolin (average particle diameter 5.2 μm), and activated clay (average particle diameter 11.7 μm). The particles were simultaneously added with polyethylene glycol 6000 as a binder, and further granulated for about 10 minutes to obtain enzyme granules C to F. As for the recovery rate of the granules C to F, 360 to 1000 μm was obtained in a high yield of 98% or more.

For comparison, two kinds of particles having different particle diameters were similarly granulated using titanium oxide (average particle diameter 0.27 μm) and water-soluble sodium sulfate (average particle diameter 16 μm). Enzyme granules G were obtained. The obtained enzyme granules C to G were stored in a detergent for clothing containing 23% of perborate as a bleaching component at 40 ° C. and a relative humidity of 80%, and the storage stability was examined. Table 3 shows the results.

[0052]

[Table 3]

From Table 3, it can be seen that the enzyme-containing granules of the present invention containing the components (a) and (b) have extremely excellent storage stability. Further, the granulated product of the present invention hardly recognized dust generation.

[0054]

EFFECTS OF THE INVENTION The enzyme-containing granules of the present invention not only have high productivity, but also have low dusting properties and high storage stability. Therefore, they are useful as detergents, especially bleach-containing detergent components. is there.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kaoru Kawamura, Kao Co., Ltd., Kasumi-gun, Kashima-gun, Ibaraki Pref. References JP-A-62-257990 (JP, A) JP-A-3-111497 (JP, A) JP-A-3-149298 (JP, A) JP-A-61-168698 (JP, A) JP-A-1 -281085 (JP, A) JP-B 46-2033 (JP, B1) JP-B 63-503390 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 3/386 C11D 3/395 C11D 17/06

Claims (17)

(57) [Claims] (1) water-insoluble or poorly-soluble inorganic particles having an average particle diameter of 1 to 100 μm;
(B) water-insoluble or hardly soluble inorganic particles having an average particle size of 0.01 to 0.8 μm and (c) a binder, (a):
(B) An enzyme-containing granule, wherein a coating layer having a weight ratio of 1: 0.1 to 1: 1 is formed. 2. The granulated product according to claim 1, wherein the granule containing the enzyme contains the enzyme and water-soluble substance particles having a particle size of 0.2 to 1.2 mm. 3. The granulated product according to claim 1, wherein the granular material containing the enzyme contains the enzyme, water-soluble substance particles having a particle size of 0.2 to 1.2 mm, and a binder. 4. The granulation according to claim 2, wherein the water-soluble substance particles having a particle size of 0.2 to 1.2 mm are particles of a substance selected from sodium chloride, potassium chloride, sodium sulfate, sodium carbonate and sugar. Stuff. 5. The talc particles according to claim 1, wherein (a) the water-insoluble or poorly-soluble inorganic particles having an average particle size of 1 to 100 μm.
The granulated product according to any one of claims 4 to 4. 6. The granulated product according to claim 1, wherein the formation of the coating layer is performed by stirring tumbling granulation. 7. The granulated product according to claim 1, wherein the preparation of the granular material containing the enzyme and the formation of the coating layer are performed by agitating tumbling granulation. 8. An enzyme-containing powdery or granular material comprising: (a) water-insoluble or poorly soluble inorganic particles having an average particle size of 1 to 100 μm;
(B) water-insoluble or hardly soluble inorganic particles having an average particle size of 0.01 to 0.8 μm and (c) a binder, (a):
(B) A method for producing an enzyme-containing granule, wherein a coating layer having a weight ratio of 1: 0.1 to 1: 1 is formed. 9. The method for producing a granulated product according to claim 8, wherein the granular material containing the enzyme contains the enzyme and water-soluble substance particles having a particle size of 0.2 to 1.2 mm. 10. The method for producing a granulated product according to claim 8, wherein the granule containing the enzyme contains the enzyme, water-soluble substance particles having a particle size of 0.2 to 1.2 mm, and a binder. 11. The water-soluble substance particles having a particle size of 0.2 to 1.2 mm are particles of a substance selected from sodium chloride, potassium chloride, sodium sulfate, sodium carbonate and sugar.
Or a method for producing a granulated product according to item 10. 12. The method for producing a granulated product according to claim 8, wherein (a) the water-insoluble or hardly soluble inorganic particles having an average particle diameter of 1 to 100 μm are talc particles. 13. The method for producing a granulated product according to claim 8, wherein the formation of the coating layer is performed by stirring and rolling granulation. 14. The method for producing a granulated product according to claim 8, wherein the preparation of the granular material containing the enzyme and the formation of the coating layer are performed by agitated tumbling granulation. 15. A detergent composition comprising the enzyme-containing granulated product according to claim 1 and a surfactant. 16. The cleaning composition according to claim 15, further comprising a bleaching agent. 17. A bleaching composition comprising the enzyme-containing granulated product according to claim 1 and a bleaching agent.