JP2008037946A - Powdery detergent enhancer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powdery detergent enhancer which has excellent storage stability and, when added to a powder detergent, exhibits improved enzyme activity even in the presence of a bleach, to provide a powder detergent composition containing the same, and to provide a method for producing the powdery detergent enhancer. <P>SOLUTION: Provided are a powdery detergent enhancer containing 1-70 mass% enzyme granules (A) having an optimal pH of 6-12, 20-90 mass% acidic particles (B) having a pH of 2-6 in a 1 mass% aqueous solution or dispersion, and 10-80 mass% inorganic particles (B) having a pH of 6-12 in a 1 mass% aqueous solution or dispersion, a powdery detergent composition containing the same, and a method for producing the powdery detergent enhancer comprising mixing ingredients (A), (C), and (B) in the given order. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an enhancer for powder detergents, and more particularly, to an enhancer for powder detergents excellent in storage stability and enzyme activity, a powder detergent composition containing the same, and a method for producing the enhancer for powder detergents.

The enhancer for powder detergent is blended in the powder detergent in order to enhance the detergency of the powder detergent for clothing. Various enhancers for powder detergents are often mixed with various enzymes in order to remove dirt such as insoluble proteins and lipids that are difficult to remove only by the action of the surfactant in the detergent. These enzymes are usually prepared in the form of powder or granules so as not to be inactivated during storage and to exhibit sufficient activity in the washing solution.
In addition, studies have been made to prevent enzyme deactivation. For example, Non-Patent Document 1 reports on the formulation of a cleaning component in which a proteolytic enzyme is difficult to deactivate. Patent Document 1 discloses a detergent composition containing a reducing agent in order to prevent enzyme deactivation due to dissolved chlorine in tap water. These techniques aim to suppress the inactivation of the enzyme in the cleaning solution, and do not improve the activity of the enzyme.

On the other hand, oxygen-based bleaching agents and bleach activators such as sodium percarbonate and sodium perborate have been blended into powder detergents for cases where the clothes are very dirty. However, when a bleaching agent, bleach activator, cleaning builder, etc. are mixed, the stability of the enzyme is lowered. Especially when a bleaching agent and a bleach activator are mixed, the enzyme activity is significantly lowered and the enzyme activity is fully exhibited. There was a problem that I could not.
Therefore, a granular enzyme composition (Patent Document 2) in which the core of the enzyme is coated with a protective agent containing an alkaline buffer salt having a pH of 7 to 11 for the purpose of preventing a decrease in enzyme activity of the enzyme-containing granulated product, and a hydrase enzyme nucleus There has been proposed a bleaching composition (Patent Document 3) in which enzyme grains are formed by coating a water-soluble alkali metal silicate and a transition metal, a protective agent such as a reducing agent.
However, in the conventional enzyme stabilization method, in order to sufficiently stabilize the enzyme, the coating layer is thickened or a water-insoluble substance is mixed in a large amount in the coating agent. As a result, there was a problem in that the ability of the enzyme to exert sufficient detergency during washing was reduced.

L. Kravetz etc. J. Am. Oil. Chem. Soc., 62, 943 (1985) Japanese Examined Patent Publication No. 47-20235 JP-A 62-79298 Japanese Patent Laid-Open No. 3-149298

  The present invention relates to a powder detergent enhancer that has excellent storage stability and can improve enzyme activity even in the presence of a bleaching agent when added to a powder detergent, a powder detergent composition containing the same, and a powder detergent enhancer It is an object to provide a manufacturing method.

The present inventors improve storage stability by blending enzyme granules and acidic particles and inorganic particles having a pH in a specific range at a specific ratio, and when used by adding to a powder detergent, And found that the enzyme activity can be improved as compared with the enzyme alone.
That is, the present invention provides the following (1) to (3).
(1) Enzyme granules (A) having an optimum pH of 6 to 12 (A) 1 to 70% by mass, 1% by mass of an aqueous solution or aqueous dispersion of acidic particles (B) 20 to 90 having a pH of 2 to 6 The enhancer for powder detergents containing 10-80 mass% of inorganic particles (C) whose pH of 6 mass% and 1 mass% aqueous solution or aqueous dispersion is 6-12.
(2) A powder detergent composition containing the enhancer for powder detergent of (1).
(3) The manufacturing method of the enhancer for powder detergents of the said (1) which mixes the said acidic particle (B) after mixing the said enzyme granulated material (A) and the said inorganic particle (C).

The enhancer for powder detergents of the present invention is excellent in storage stability, and when added to a powder detergent, the enzyme activity can be improved in the washing solution even in the presence of a bleaching agent as compared with the enzyme alone. The detergency of the detergent composition can be greatly improved.
Moreover, according to the manufacturing method of this invention, the enhancer for powder detergents excellent in storage stability and enzyme activity can be manufactured simply.

(Enhancer for powder detergent)
The enhancer for powder detergent of the present invention has an enzyme granulated product (A) having an optimum pH of 6 to 12 (hereinafter, simply referred to as “enzyme granulated product (A)”) 1 to 70% by mass, 1% by mass. 20 to 90% by mass of acidic particles (B) (hereinafter, simply referred to as “acidic particles (B)”) whose pH of the aqueous solution or aqueous dispersion is 2 to 6, and the pH of the aqueous solution or aqueous dispersion of 1% by mass It is characterized by containing 10-80 mass% of inorganic particles (C) (hereinafter, simply referred to as “inorganic particles (C)”) having a particle diameter of 6-12.
In the present invention, “powder” is a concept including powder, granules and the like.

The enzyme granulated product (A) used in the present invention is not particularly limited as long as the optimum pH is 6 to 12. Preferably, at least one selected from proteolytic enzymes (proteases), lipolytic enzymes (lipases), cellulose-degrading enzymes (cellulases), starch-degrading enzymes (amylases), and pectin-degrading enzymes (pectinases) can be mentioned. There are no particular restrictions on the type, origin and purity of the enzyme.
Here, “optimal pH” means that the relative activity is 50% or more when the enzyme activity related to the enzyme granulated product (A) is measured under the condition that the substrate is constant and the pH is varied. Means the pH range. The optimum pH of the enzyme granulated product (A) is preferably 7 to 11 and more preferably 8 to 11 from the viewpoints of detergency enhancement and storage stability.

The proteolytic enzyme preferably has serine at the active center and has an optimum pH of 7 or more, particularly 8 to 11.
Examples of the proteolytic enzyme include alkaline proteases KAP4.3G and KAP13.1G (registered trademark of Kao Corporation) manufactured by Kao Corporation, Alcalase, Esperase, Savinase, Everase (Novazymes Corporation) Everlase) (Novozymes registered trademark), Genencor Maxacal, Maxapem, Purafect, Opticlean, Properase (Genencore registered trademark), etc. Is mentioned. In particular, from the viewpoint of storage stability, alkaline protease KAP from Kao Corporation and sabinase from Novozymes are preferred.
Here, the optimum pH of the proteolytic enzyme means a region where the relative activity shows 90% or more when the enzyme activity is measured under the condition where the pH is changed by the casein method. Details of the casein method are given in the examples.

Cellulolytic enzymes include bacterial cellulases and fungal cellulases. The optimum pH of the cellulolytic enzyme is preferably 6-12, more preferably 7-11. Such a weak alkaline activity cellulose-degrading enzyme has a function of acting on the amorphous cellulose of the fiber in a weakly lyrical washing water to easily remove the dirt on the fiber surface.
As the cellulolytic enzyme, for example, those described in JP-A 63-264699, page 4, upper right column, line 13 to page 5, lower right column, line 12 can be used. It is preferable to use an alkaline cellulase obtained from Bacillus sp. KSM-635 (FERM BP-1485) or a mutant thereof. Moreover, the cellulase described in JP-A-8-53699, paragraph [0015] can also be used. More specifically, enzyme granulated products such as KAC500 (registered trademark) manufactured by Kao Corporation and Cellzyme (registered trademark) manufactured by Novozymes can be mentioned.
Here, the optimum pH of the cellulolytic enzyme means a region in which the relative activity is 50% or more when the enzyme activity is measured under conditions where the pH is varied using carboxymethylcellulose (CMC) as a substrate. Cellulase enzyme activity is measured by the 3,5-dinitrosalicylic acid (DNS) method, the details of which are shown in the examples.

The lipolytic enzyme is not particularly limited, but an alkaline lipase having an optimal enzyme activity pH of 8 to 11 is preferred. Examples thereof include LIPOLASE100T, LIPOLASE ULTRA, LIPEX (registered trademark of Novozymes), KAM-9.0 (registered trademark of Kao Corporation) and the like manufactured by Novozymes.
Starch-degrading enzymes are not particularly limited, and include α-amylase, β-amylase, etc. Alkaline α-amylase having an optimum enzyme activity pH of 6 to 10 is preferred.
Among the above-mentioned enzymes, it is preferable to include at least a proteolytic enzyme, and it is more preferable to include a cellulose-degrading enzyme. When a proteolytic enzyme and a cellulolytic enzyme are used in combination, the mass ratio of (cellulolytic enzyme / proteolytic enzyme) is preferably 20/1 to 1/20, more preferably 10/1 to 1/1 / as the enzyme bulk powder. 10.
The enzyme content in the enzyme granulated product (A) is not particularly limited and may vary depending on the type, but is usually 0.1 to 5% by mass, preferably 0.1 to 2% by mass. If the enzyme content is within the above range, the detergency can be sufficiently reinforced and the problem of unpleasant odor due to the excessive enzyme content does not occur.

There is no restriction | limiting in particular in the manufacturing method of an enzyme granulated material (A). For example, binders necessary for granulation, enzyme stabilizers, adsorbents for adsorbing odorous components derived from enzyme culture, coloring agents, etc. are added by the method described in JP-A-62-2579990 Then, dry granulation can be performed using a stirring tumbling granulator.
As the binder, a water-soluble organic binder is preferable. For example, (a) a water-soluble polymer such as polyethylene glycol having a melting point of 35 ° C. or higher and a derivative thereof, polyoxyethylene / polyoxypropylene copolymer, (b) a melting point or Nonionic surfactants having a pour point of 35 ° C. or higher, (c) polycarboxylates having an average molecular weight of 4000 or higher, and the like.

The acidic particles (B) are not particularly limited as long as the pH of the 1% by mass aqueous solution or aqueous dispersion is 2 to 6. Preferably, it is acidic particle | grains (B) whose pH of 3 mass% aqueous solution or aqueous dispersion is 3-6.
Examples of the acidic particles (B) include solid or powdered inorganic acids, organic acids, salts thereof, and zeolites that exhibit solid acidity. More specifically, one or more kinds of particles selected from low molecular weight organic acids such as formic acid, succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid, p-hydroxybenzoic acid, and salts thereof may be mentioned. It is done. In the case of a salt, the counter ion is preferably an alkali metal ion or an ammonium ion.
Among these, one or more kinds of particles selected from succinic acid, citric acid and salts thereof are particularly preferable. When these low molecular weight organic acids and their salts are used, bubbles generated from the powder detergent particles are thermally expanded due to heat of hydration and heat of dissolution generated by the reaction of the organic acids and their salts with water. It is more preferable at the point which can accelerate | stimulate disintegration property of powder detergent particle | grains by it.
Said acidic particle (B) can be used individually or in mixture of 2 or more types.

The inorganic particles (C) function to reduce the contact between the enzyme granulated product (A) and the acidic particles (B) and prevent the activity of the enzyme granulated product (A) from decreasing. In the three-component system of enzyme granulated product (A), acidic particle (B), and inorganic particle (C), the enzyme activity of enzyme granulated product (A) is improved as compared with the case of enzyme alone.
The inorganic particles (C) are not particularly limited as long as the 1% by mass aqueous solution or aqueous dispersion has a pH of 6-12. Preferably, the inorganic particles (C) have a 1% by mass aqueous solution or aqueous dispersion having a pH of 7 to 11, more preferably 8 to 11.
As the inorganic particles (C), an alkaline builder generally used for a laundry detergent can be used. For example, zeolite (A type, X type, P type), amorphous aluminosilicate, carbonate, sulfate, tripolyphosphate, pyrophosphate, crystalline silicate and the like can be mentioned. The average particle size of the inorganic particles (C) can be appropriately determined in consideration of the average particle size of the enzyme granulated product (A) and the acidic particles (B).
Among these, an A-type zeolite having an average particle size of 0.1 to 10 μm, preferably 0.1 to 5 μm, an average particle size of 10 to 800 μm, preferably 50 to 300 μm, sodium carbonate, an average particle size of 10 to 800 μm, preferably Is preferably one or more particles selected from 50 to 300 μm sodium sulfate and an average particle size of 5 to 800 μm, preferably 10 to 150 μm sodium tripolyphosphate.
Said inorganic particle (C) can be used individually or in mixture of 2 or more types.

The content and mass ratio of the enzyme granulated product (A), acidic particles (B), and inorganic particles (C) in the enhancer for powder detergents of the present invention are from the viewpoints of detergency enhancement and storage stability. It is as follows.
Content of enzyme granulated material (A) is 1-70 mass%, Preferably it is 2-50 mass%, More preferably, it is 3-45 mass%.
Content of an acidic particle (B) is 20-90 mass%, Preferably it is 30-85 mass%, More preferably, it is 30-80 mass%.
Content of an inorganic particle (C) is 10-80 mass%, Preferably it is 10-70 mass%, More preferably, it is 12-65 mass%.
The mass ratio of [acid particles (B) / enzyme granulated product (A)] is preferably 0.1 to 20, more preferably 0.5 to 15, and particularly preferably 0.8 to 12.
The mass ratio of [inorganic particles (C) / [enzyme granulated product (A) + acidic particles (B)]] is preferably 0.05 to 5.0, more preferably 0.05 to 3.0. Especially preferably, it is 0.1-2.0.

(Production method of enhancer for powder detergent)
There is no restriction | limiting in particular in the manufacturing method of the enzyme granule (A), acidic particle (B), and inorganic particle (C) used for the enhancer for powder detergents of this invention. For example, in addition to the above, the spray drying method, the dry neutralization method, and the dry granulation method described in the “Patent Office Gazette of Known and Conventional Techniques (Clothing Detergent for Clothing)” (issued on March 26, 1998 by the Patent Office) , Dry granulation method, wet granulation / drying method, dry blend method and the like.
The enhancer for powder detergents of the present invention can be obtained by mixing a predetermined amount of the obtained components (A) to (C). Although there is no restriction | limiting in particular in the mixing order of (A)-(C) component, the contact with an enzyme granulation (A) and acidic particle (B) is reduced, and the activity fall of an enzyme granulation (A) is reduced. From the viewpoint of prevention, it is preferable to mix the acidic particles (B) after mixing the enzyme granulated product (A) and the inorganic particles (C).
That is, the method for producing an enhancer for a powder detergent according to the present invention is characterized in that the enzyme granulated product (A) and the inorganic particles (C) are mixed and then the acidic particles (B) are mixed.
It should be noted that an appropriate amount of a known additive such as an enzyme stabilizer can be added to the enhancer for a powder detergent of the present invention as long as the effects of the present invention are not impaired. Examples of enzyme stabilizers include calcium salts and magnesium salts of reducing agents (sodium sulfite and sodium hydrogen sulfite), polyols, boron compounds, and the like. The reducing agent stabilizes the enzyme by removing chlorine in tap water, and also has an effect as an antioxidant.

The average particle size of the enzyme granulated product (A), acidic particles (B), inorganic particles (C), and powder detergent enhancer used in the present invention is determined in terms of storage stability and solubility in the cleaning liquid, and From the relationship with other components to be blended and the average particle size of the powder detergent particles, it is as follows.
The average particle diameter of the enzyme granulated product (A) is preferably 100 to 2000 μm, more preferably 200 to 1500 μm. The average particle diameter of the acidic particles (B) is preferably 100 to 2000 μm, more preferably 200 to 1000 μm. The average particle diameter of the inorganic particles (C) is as described above.
The average particle size of the enhancer for powder detergents of the present invention is preferably 100 to 900 μm, more preferably 150 to 800 μm, and particularly preferably 200 to 700 μm.
In addition, said average particle diameter is a value calculated | required from the weight fraction by the size of a mesh after vibrating for 5 minutes using the standard sieve of JISZ8801-1 (2000).

(Powder detergent composition)
The powder detergent composition of the present invention contains the enhancer for powder detergent of the present invention.
When the enhancer for a powder detergent of the present invention is added to a powder detergent composition containing a surfactant as a main component or a powder detergent composition containing a surfactant and a bleaching agent, the detergency of the powder detergent composition is greatly increased. Can be improved. In addition, the enzyme stability is excellent even in the presence of a bleaching agent, and an enzyme activity superior to that of the enzyme alone can be exhibited in the cleaning solution.
The enhancer for powder detergents of the present invention can be suitably used as a detergency enhancer for powder detergent compositions for clothing, automatic dishwashers, and dwellings. Moreover, the enhancer for powder detergents of this invention can also be used as a fiber pretreatment agent.

The following are mentioned as surfactant used for the detergent composition for clothes.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, alkane sulfonate, fatty acid salt, alkyl or alkenyl ether carboxylate. , Alkyl or alkenyl phosphate esters or salts thereof. Among these, an alkylbenzene sulfonate having 10 to 18 carbon atoms or an alkyl sulfate having 10 to 18 carbon atoms is preferable. The counter ion is preferably sodium, potassium or ammonium, particularly preferably potassium or sodium.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide, or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoside, fatty acid glycerin monoester, alkyl An amine oxide etc. are mentioned. Among these, polyoxyalkylene alkyls or alkenyl ethers having a total carbon number of 10 to 18 and an ethylene oxide addition mole number of 5 to 15 are preferred from the viewpoint of oil stain detergency.
The HLB value (calculated by the Griffin method) of these nonionic surfactants is preferably 10.5 to 15.0, more preferably 11.0 to 14.5.

Examples of amphoteric surfactants include betaine-type amphoteric surfactants such as alkyl (preferably 8-20 carbon atoms) betaines, imidazolinium betaines, and sulfonic acid-type amphoteric surfactants. And quaternary mono-long-chain alkyl ammonium salts and di-long-chain alkyl ammonium salts having a long-chain alkyl group having 8 to 18 carbon atoms.
Among these, anionic surfactants and nonionic surfactants are preferred, and the mass ratio of (anionic surfactant / nonionic surfactant) is preferably 10/0 to 1/10, more preferably 10 / 0 to 2/10, particularly preferably 10/0 to 5/10.

As the bleaching agent, oxygen-based bleaching agents composed of inorganic peroxides such as percarbonates such as sodium percarbonate and perborates such as sodium perborate are preferable. When a percarbonate is used in a composition containing zeolite, for example, a percarbonate coated with at least one selected from paraffin, borate, perborate, ethylene oxide adduct of alcohol, polyethylene glycol, and silicate compound is used. preferable.
In order to supplement the bleaching power of the oxygen bleach, a bleach activator can be blended. There is no restriction | limiting in particular as a bleaching activator, For example, tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycolyl, alkanoyl or alkenoyl (carbon number 8-14) oxybenzene carboxylic acid or its salt, alkanoyl or alkenoyl (carbon number 8) -14) Examples include oxybenzene sulfonate. In particular, decanoyloxybenzenecarboxylic acid or a sodium salt thereof, and dodecanoyloxybenzenesulfonic acid sodium salt are preferred.

  Powder detergent compositions include known detergent ingredients, for example, inorganic builders such as crystalline aluminosilicate, orthophosphate, pyrophosphate, tripolyphosphate; nitrilotriacetate, ethylenediaminetetraacetate, citrate, Organic builder such as isocitrate; alkaline agent such as silicate, carbonate, sesquicarbonate; polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyacrylate, acrylic acid-maleic acid copolymer or salt thereof An anti-staining agent can be blended, and an anti-caking agent, a fluorescent dye, a bluing agent, a photoactivated bleach, a fragrance, and the like can also be blended.

The blending amount in the powder detergent composition is usually from 5 to 60% by mass, preferably from 5 to 40% by mass, and from 1 to 50% by mass, preferably from 5 to 40% by mass, from the viewpoint of cleaning performance and solubility. -40% by weight, alkali agent is usually 1-50% by weight, preferably 5-40% by weight, bleaching agent is usually 1-20% by weight, preferably 1-10% by weight, bleach activator is usually 0-20%. % By weight, preferably 1 to 10% by weight, 0 to 10% by weight of anti-staining agent, preferably 0.1 to 5% by weight, and 0 to 10% by weight of fluorescent dye, preferably 1 to 5% by weight The fragrance is usually contained in an amount of 0 to 5% by mass, preferably 0.01 to 3% by mass.
The enhancer for a powder detergent of the present invention is preferably blended in the powder detergent composition in an amount of 0.5 to 50% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass. If content of the enhancer for powder detergents of this invention is in the said range, detergency will be enough and the problem of unpleasant odor generation by having too much enzyme content will not arise.
The average particle size of the powder detergent composition containing the enhancer for powder detergent of the present invention is preferably from 150 to 800 μm, more preferably from 200 to 700 μm, particularly preferably from the viewpoints of prevention of pasting at the time of dissolution and solubility. Is 250 to 650 μm.

Examples 1-11 and Comparative Examples 1-9
Prepare the components (A), (B), and (C) shown in Table 1 [the total amount of (A) to (C) is 50 to 80 kg], and a drum shaker with an internal volume of 200 L (manufactured by Oari Corporation) The components (A) and (C) were added to and mixed, and (B) was added. The mixture was further mixed at 12 rpm for 10 minutes, then stored at 40 ° C. for 3 days, and the enzyme activity was measured by the following method. The results are shown in Table 1.

[Method for measuring protease activity (casein method)]
Enzyme solution (3.0 × 10 ⁻⁵ mP.U) 0.1 mL was mixed with 0.9 mL of 50 mM borate-NaOH buffer (pH 10.5) containing 1.1% casein, and reacted at 30 ° C. for 15 minutes. Then, 2 mL of a reaction stop solution (0.123 M trichloroacetic acid / 0.246 M sodium acetate / 0.369 M acetic acid) was added and allowed to stand for 20 minutes. Next, the reaction solution was filtered with a filter paper (No. 2 manufactured by Whatman Co.), and the protein degradation product (amino acid) in the filtrate was quantified by the Raleigh method. Enzyme activity was shown as a relative value with Comparative Example 1 (alkaline protease granule as component (A) alone) as 100%.
One unit of enzyme (1 P.U) was defined as the amount of enzyme that liberates an acid-soluble proteolysate corresponding to 1 μmol of tyrosine per minute under the above reaction conditions.

The symbols in Table 1 are as follows.
A-1: Alkaline protease granulated product (Kao Corporation, KAP13.1G, optimum pH 8-11, average particle size 700 μm)
B-1: Succinic acid particles (pH 3.9 of 1% by mass aqueous solution, average particle size 900 μm)
B-2: Citric acid particles (pH 2.25 of 1% by weight aqueous solution, average particle size 796 μm)
C-1: A-type zeolite particles (Zeobuilder, ZEOLITE-POWDER, pH 11.13 of a 1% by mass aqueous dispersion, average particle size 2.9 μm)
C-2: Sodium carbonate particles (light ash, pH 11.27 of 1% by weight aqueous solution, average particle size 100 μm)
C-3: sodium tripolyphosphate particles (pH 9.50 of 1% by mass aqueous solution, average particle size 100 μm)
C-4: Sodium sulfate particles (pH 7.05 of 1% by weight aqueous solution, average particle size 276 μm)

The powder detergent composition was prepared as follows, and the enhancer for powder detergent obtained above was added, and the cleaning power of the powder detergent was evaluated by the following cleaning power evaluation method. The results are shown in Table 1.
[Preparation of powder detergent composition]
The composition of the powder detergent composition is 25% by mass of linear sodium alkylbenzene sulfonate (alkyl group having 12 to 14 carbon atoms), polyoxyethylene alkyl ether (alkyl group having 12 to 14 carbon atoms, ethylene oxide average added mole number 7). Nonionic surfactant) 3% by mass, 4A-type zeolite (Zeobuilder, average particle size 2.9 μm) 8% by mass, sodium tripolyphosphate 20% by mass, sodium carbonate 29% by mass, sodium sulfate 6.0% by mass %, Polyoxyethylene (molecular weight 13000) 0.5%, acrylic acid-maleic acid copolymer sodium salt [70 mol% neutralized, acrylic acid / maleic acid (molar ratio) = 3/7, average molecular weight 70,000] 3 mass %, [Chinopearl CBS-X / Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals)] 1/1 mixture (fluorescent whitening agent) 0.1 wt%, sodium percarbonate (bleach) 2 wt%, and was adjusted to moisture 3.4 wt%.

[Evaluation method of cleaning power]
Dissolve 1 g of the powder detergent composition obtained above in 1 L of water, add a powder detergent enhancer diluted to 100 times water to the value shown in the table, and add artificial contamination cloth (EMPA116, Testfabrics Inc. 5), wash water hardness: 4 ° DH, wash water temperature: 20 ° C., rotation speed: 100 rpm, wash time: 5 minutes, rinse: 5 minutes (1 L, tap water) Washed with.
The detergency of the powder detergent was determined by measuring the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation), and obtaining the cleaning rate (%) by the following formula: Evaluation was carried out by obtaining the measurement average value of 5 sheets.
Washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)] × 100

Example 12
In Example 1, a powder detergent composition was prepared in the same manner as in Example 1 except that (A) component and (B) component were mixed in advance and then (C) was added and further mixed. The results of evaluating the force are shown in Table 1.

Example 13
In Example 1, alkaline protease granulated product (a-1) and alkaline cellulase granulated product (a-2) (manufactured by Kao Corporation, KAC500, optimum pH 7-11, average particle size 700 μm as enzyme granulated product. Table 1 shows the results of preparing a powder detergent composition in the same manner as in Example 1 and evaluating the enzyme activity and the detergency, except that in combination.
Cellulase activity was measured by the following method.
[Method for measuring cellulase activity (3,5-dinitrosalicylic acid (DNS) method)]
0.2 mL of 0.5 M glycine-sodium hydroxide buffer (pH 9.0), 0.4 mL of 2.5% (w / v) carboxymethylcellulose (manufactured by Nippon Paper Industries Co., Ltd., trade name: A01MC), After adding 0.1 mL of an appropriately diluted enzyme solution to a reaction solution consisting of 3 mL of deionized water and reacting at 40 ° C. for 20 minutes, 1 mL of dinitrosalicylic acid reagent (0.5% dinitrosalicylic acid, 30% Rochelle salt, 1.6% aqueous sodium hydroxide solution) was added, and reducing sugar was developed in boiling water for 5 minutes. After quenching in ice water, 4 mL of deionized water was added and the absorbance at 535 nm was measured to determine the amount of reducing sugar produced. In addition, after adding a dinitrosalicylic acid reagent to the reaction liquid processed without adding an enzyme liquid, the blank added the enzyme liquid and prepared the same color.
One unit of enzyme (1 U) was defined as the amount of enzyme that produces a reducing sugar corresponding to 1 μmol of glucose per minute under the above reaction conditions.

  In Table 1, in Comparative Examples 1-9, the enzyme activity is 25-100, which is much lower than that of the enzyme alone (enzyme activity 100), and the washing rate is 30-40%. In contrast, the enhancers for powder detergents of Examples 1 to 13 have an enzyme activity of 105 to 110, excellent storage stability, and an enzyme activity of 5 to 10% than that of the enzyme alone (enzyme activity 100). It can be seen that the cleaning rate is improved and 50 to 55%.

Claims (7)

  Enzymatic granulated product (A) having an optimum pH of 6 to 12 (A) 1 to 70% by mass, 1% by mass of an aqueous solution or aqueous dispersion having an acidic particle (B) of 2 to 6 in an amount of 20 to 90% by mass, And a reinforcing agent for a powder detergent containing 10 to 80% by mass of inorganic particles (C) having a pH of 6 to 12 in a 1% by mass aqueous solution or aqueous dispersion.   The enhancer for powder detergents of Claim 1 whose enzyme granulated material (A) is a granulated material containing 1 or more types chosen from a protease, a lipolytic enzyme, and a cellulose degrading enzyme.   The enhancer for powder detergents of Claim 1 or 2 whose acidic particle (B) is 1 or more types of particle | grains chosen from a succinic acid, a citric acid, and those salts.   The enhancer for powder detergents in any one of Claims 1-3 whose inorganic particle (C) is 1 or more types of particle | grains chosen from A-type zeolite, sodium carbonate, sodium sulfate, and sodium tripolyphosphate.   The enzyme granulated product (A) is 2 to 50% by mass, the acidic particles (B) are 30 to 85% by mass, and the inorganic particles (C) are 10 to 70% by mass. Enhancer for powder detergents.   The powder detergent composition containing the enhancer for powder detergents in any one of Claims 1-5.   The manufacturing method of the enhancer for powder detergents of Claim 1 which mixes the said acidic particle (B) after mixing the said enzyme granulated material (A) and the said inorganic particle (C).