JP2006143855A - Amylase-containing bleaching composition with improved effect for removing drink stain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching composition highly effective for removing drink stains such as tea and red wine, even through normal washing, and a method for removing drink stains. <P>SOLUTION: The bleaching composition contains an amylase with an amylase relative activity of ≥120%, wherein the amylase relative activity is calculated by formula (1): amylase activity (%)=[(reflectivity after testing-reflectivity before testing)/(reflectivity of the original cloth-reflectivity before testing)]×100 and formula (2): amylase relative activity (%)=[amylase activity of an amylase-containing aqueous solution/amylase activity of a control test cloth]×100. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an amylase-containing bleaching composition that can be used for clothing and the like, and more particularly to a bleaching composition having a high effect of removing stains from beverage stains such as tea and red wine. The present invention also relates to a method for removing beverage stain stains.

In recent years, detergents for clothing having a bleaching effect have been favorably used because they can effectively remove stains such as tea, red wine, coffee and fruit juice simultaneously with removal of lipid stains attached to clothing. As the bleaching agent, oxygen-based bleaching agents are widely used because they do not lose color even when applied to colored clothes for clothing, and sodium percarbonate is representative. Recently, a bleach activator is used in combination as a base for enhancing the bleaching effect. On the other hand, many researches on a bleach catalyst composed of a transition metal and a ligand have been made.
It is well known that bleach activators are converted to organic peracids by reacting with hydrogen peroxide, resulting in high bleaching power on stain stains.
A method using a bleaching catalyst is described in Nature, VOL. 369 (1994) pp. 637-639 and J.P. Am. Chem. Soc. , VOL. 115 (1993) pp. 1772 to 1773 (non-patent documents 1 and 2), and the complex catalytically activates hydrogen peroxide in the bleaching solution and reacts with the dye to cause high bleaching effect on stain stains. A mechanism has been proposed. Therefore, high bleaching power can be efficiently obtained with a small amount of complex.
On the other hand, in order to remove stain stains, an enzyme such as amylase is also used.
However, conventional amylases have an effect on food stains such as curry and beef stew, which are high in starch, but cannot be removed at all with detergent alone. Beverage stains derived from beverages such as tea, red wine, coffee and fruit juice An effect on dirt cannot be expected, and an amylase that exhibits high effects on both food stains and beverage stains has been desired.

Nature, VOL. 369 (1994) 637-639 J. et al. Am. Chem. Soc. , VOL. 115 (1993) 1772-1773.

  In view of the above circumstances, an object of the present invention is to provide a bleaching composition and a method for removing beverage stain stains that are highly effective for beverage stain stains such as tea and red wine even by ordinary washing.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using an inorganic peroxide that releases hydrogen peroxide in water and a bleach catalyst and amylase, The present invention has been completed.
That is, the present invention provides (A) a bleaching composition comprising amylase having an amylase relative activity of 120% or more calculated according to the following formulas (1) and (2).

The present invention is also a method for removing beverage stain stains,
(I) preparing an amylase having an amylase relative activity of 120% or more calculated according to the following formulas (1) and (2);

(Ii) adding the amylase prepared in step (i) to basic adjusted water to prepare a basic aqueous solution containing amylase; and (iii) containing the amylase obtained in step (ii) Treating a textile product having a beverage stain with a basic aqueous solution;
A method for removing the beverage stain soil is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the removal method and bleaching composition excellent in the removal performance with respect to drink stain stains, such as black tea, red wine, coffee, and fruit juice, are obtained. According to the present invention, an excellent removal effect is also obtained for food and beverage stain stains containing starch such as curry, beef stew and cocoa, and food and beverage stain stains containing glycoproteins such as squid ink.

The object of removal according to the present invention is mainly beverage stain stains, and beverages that form stains include tea, red wine, coffee, fruit juice, Japanese tea, milk, and the like.
(A) component (A) component of this invention is amylase whose amylase relative activity computed according to following formula (2) is 120% or more. The relative activity of amylase can be determined as follows.
(I) Preparation of test cloth 0.15 mL of red wine (Suntory Reserve) was dropped on an oil-based cooperative fabric (5 × 5 cm, obtained from the Laundry Science Association) and indoors (25 ° C., humidity 60%) for 12 hours. Use a dry test cloth.
(Ii) Preparation of amylase-containing aqueous solution A 25 ° C. solution in which amylase is diluted 1000 times with 3 degree hard water (German hardness) is prepared. On the other hand, 500 mL of 25 degreeC 3 degree hard water (German hardness) each containing 150 ppm of sodium carbonate and sodium hydrogencarbonate is prepared. In addition, pH of the obtained aqueous solution is 10 (25 degreeC). Here, a 1000-fold diluted solution of amylase prepared in advance is added so that the weight of enzyme protein is 0.15 mg to obtain an amylase-containing aqueous solution.
As a control aqueous solution, 25 ° C., pH 10, 3 degree hard water (German hardness) each containing 150 ppm of sodium carbonate and sodium hydrogen carbonate is used.

(Iii) Amylase activity test Two test cloths prepared in step (i) are immersed in the amylase-containing aqueous solution prepared in step (ii) and left for 30 minutes. The liquid temperature is kept at 25 ° C. during standing. After leaving for 30 minutes, two test cloths are taken out, immersed in 2 L of ion exchange water, and rinsed by stirring for 1 minute by hand. After rinsing twice in the same procedure, the amylase activity test is performed by drying in a light-shielded room (25 ° C., humidity 60%) for 12 hours.
Test the control fabric in the same manner except that the control aqueous solution was used.
(Iv) Measurement of amylase activity and relative activity The amylase activity was measured by measuring the reflectance (WB value) of the test cloth before and after the test using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Σ2000, using a 460 nm cut filter). Calculation is performed by substituting the obtained reflectance into the following formula (1).

  The amylase relative activity is calculated by substituting the amylase activity obtained from the formula (1) into the following formula (2).

The amylase satisfying the specific amylase relative activity can be appropriately selected by a simple screening method using the above-described commercially available apparatus.
Examples of amylases that can be used in the present invention include α-amylase, β-amylase, α-glucosidase, and glucoamylase, α-1,6 bonds such as starch and glycogen, which hydrolyze α-1,4 bonds such as starch and glycogen. Glucoamylase, pullulanase, isoamylase, amylo-1,6 glucosidase / 4-alpha glucanotransferase, oligo-1,6-glucosidase and the like are included. It is not particularly limited as long as it is an enzyme that hydrolyzes starch, and can be used alone or in combination of two or more.
Examples of amylases that can be used in the present invention are given below. However, the following examples do not limit the present invention. Examples of commercially available enzymes include the following. Termamyl, Duramil, Stainzyme, Promozyme 200L (above, Novozymes), Maxamyl (Genencore), Amano Pharmaceutical's DB-Ranama 250, Pullulanase derived from Aerobacter aerogenes ATCC 9621 (crude or crystallized product released from Seikagaku Corporation).

In addition to the above amylase, examples of the amylase described in the patent publication include the following.
(1) Alkaline amylase derived from Bacillus described in JP-A-48-91271 (2) Alkaline amylase derived from Streptomyces described in JP-A-61-209588 (3) JP-A-62-208278 Bacillus-origin alkaline amylase described in the publication (4) Bacillus origin-origin alkali amylase described in JP-A-2-49584 (5) Bacillus-origin alkali pullulanase described in JP-A-3-87176 (6) Bacillus genus alkaline pullulanase described in JP-A-3-87177 (7) Bacillus amylase described in JP-A-3-103177 (8) Bacillus-origin alkali amylase described in JP-A-3-108482 (9) ) Alkaline amylase of the genus Bacillus described in JP-A-4-23983 (10) Alkaline amylase Bacillus origin of 4-58885 JP

(11) Alkaline amylase derived from Natronococcus described in JP-A-4-21369 (12) α-amylase derived from Bacillus described in JP-A-4-500756 (13) described in JP-A-6-14775 (2) Alkaline isoamylase of the genus Bacillus (14) Alkaline amylase of the genus Bacillus described in JP-A-8-56662 (15) Alkaline α-amylase of the genus Bacillus described in JP-A-9-206073 (16) Α-Amylase variant described in Table 10-10504197 (17) Alkaline amylase described in JP 2000-023665 (18) Alkaline amylase described in JP 2000-023666 (19) JP 2000-023667 Alkaline amylase (20) described in Japanese Patent Publication No. 2002-112792 -Amylase

(21) α-amylase derived from Pyrococcus genus described in JP-A-4-503757 (22) α-amylase derived from Bacillus genus described in JP-A-8-500003 (23) JP-A-8-504586 Α-amylase of the genus Bacillus or Asparagillus described (24) Starch-degrading enzyme of the genus Pyrococcus described in JP-A-8-506673 (25) Origin of Bacillus described in JP-A-9-503916 Α-amylase (26) α-amylase of the genus Bacillus described in JP-T 9-510617 (27) α-amylase variant described in JP-T 2001-520006 (28) JP-A 2001-521739 Α-Amylase variant (29) described in Japanese Patent Publication No. 2002-504323 No. 2002 Alkaline Bacillus amylase (30) Special Table 2002-530 Α-Amylase Variant (31) described in Japanese Patent No. 072 (alpha) -Amylase Variant (32) described in Japanese Translation of PCT International Publication No. 2002-540785 (32) Α-Amylase Mutant

  These amylases can be used alone or in combination of two or more. When two or more kinds are used in combination, even if the relative activity for each amylase is less than 120%, it can be used as the component (A) of the present invention as long as the total relative activity is 120% or more. . As the component (A) of the present invention, amylase having a relative activity of 120% or more is preferable, and amylase having 130% or more is more preferable. Without being bound by any theory, if the relative activity of amylase is 120% or more, the adhesion between the stain of the beverage stain that has entered the fiber of the clothing and the fiber can be weakened. It is considered that it exhibits a high removal effect against dirt. The relative activity of amylase can be increased by selecting an amylase having a high amylase activity or selecting an amylase that has been mutated by genetic manipulation or the like so as to increase the amylase activity. In particular, the amylases described in the above patent publications (21) to (33) are preferable. In particular, a stainzyme is preferable.

In the present invention, the amylase of component (A) is preferably used by adding 0.01 to 1 ppm as an enzyme protein concentration to an aqueous solution for removing beverage stain stains, more preferably 0.01 to 0.5 ppm. It is. If it is less than 0.01 ppm, the desired removal effect may not be obtained, and even if it is used in excess of 1 ppm, the cleaning effect may be saturated, which may not be economical.
In the present invention, in the case of a bleaching composition, (A) amylase is preferably used in combination with an alkaline agent in such an amount that the pH of a 0.05 to 0.5% aqueous solution (25 ° C.) becomes basic. Examples of the alkali agent that can be used in the present invention include sodium carbonate, sodium hydrogen carbonate, sodium silicate and the like. Of these, sodium carbonate, sodium bicarbonate, and sodium silicate are preferable. At this time, the pH of the aqueous solution is preferably 8 to 12, and more preferably 9 to 11.
(A) When mix | blending with the bleaching composition containing the amylase of a component, it is preferable to mix | blend and use 0.001-0.1 mass% as enzyme protein mass, More preferably, it is 0.001-0. 05% by mass. If it is less than 0.001% by mass, the desired removal effect may not be obtained, and even if it exceeds 0.1% by mass, the cleaning effect will be saturated, which may not be economical.
The amylase of the component (A) of the present invention is granulated with polysaccharides, minerals, polyethylene glycol, titanium oxide and the like in consideration of improvement of storage stability, improvement of aroma, beautification of appearance, safety to human body, etc. It is preferable to use it. In the case of granulating the component (A), the proportion of the component (A) in the granulated product is preferably 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass. If it is 10% by mass or more, it may be difficult to improve the aroma. The average particle size of the granulated product containing the component (A) is preferably 200 to 1000 μm, more preferably 300 to 800 μm. In order to satisfy both solubility and safety to the human body, particles having a particle size of 125 μm or less and It is preferable that the particle | grains of 1000 micrometers or more are 10 mass% or less. Here, the average particle diameter can be confirmed by a method of obtaining a particle size distribution using a sieve and calculating from the particle size distribution.

When the granulated material containing the component (A) is used in an aqueous solution for removing beverage stain stains, it is preferable to add 0.1 to 100 ppm as a granulated substance amount concentration, and more preferably, 0.1%. 1-50 ppm. If it is less than 0.1 ppm, the desired removal effect may not be obtained, and even if it is used in excess of 100 ppm, the cleaning effect may be saturated, which may not be economical.
(B) When mix | blending with the bleaching composition containing the granulated material containing a component, it is preferable to mix | blend and use 0.1-5 mass% as a granulated material, Preferably, it is 0.1-3. % By mass. If it is less than 0.1% by mass, the desired removal effect may not be obtained, and even if it exceeds 5% by mass, the cleaning effect will be saturated, which may not be economical.
The amount of enzyme protein in the composition of the present invention is determined by obtaining a crude enzyme by separation means such as salting-out method, precipitation method, ultrafiltration method, etc. Alternatively, the band formed by SDS-polyacrylamide gel electrophoresis can be stained by a known staining method, and the degree of staining can be compared with a known enzyme purified product.

(B) component (B) component of this invention is a peroxide which discharge | releases hydrogen peroxide in water. Specific examples include sodium percarbonate, sodium perborate, sodium perborate trihydrate and the like. From the viewpoint of solubility during use and stability during storage, sodium percarbonate may be used. preferable. A commercially available product can be used as the percarbonate, and specific examples include sodium percarbonate sold by Mitsubishi Gas Chemical Co., Ltd. under the trade names SPC-Z and SPC-G. When used as a cleaning agent containing zeolite or containing a relatively large amount of water, for example, 3% or more, it is preferable to use sodium percarbonate stabilized by coating with an inorganic or organic compound. Examples of the coating agent include boric acid or borate, amorphous silicate, magnesium salt, or water-insoluble organic compounds such as paraffin and wax. The coated sodium percarbonate can be produced by a known method. For example, in addition to JP-A-59-196399 and USP4526698 (both sodium percarbonate is coated with borate), JP-A-4-31498 And JP-A-6-40709 and JP-A-7-11803. Commercially available products can also be used as the coated sodium percarbonate. Specific examples include those sold under the trade name SPC-D by Mitsubishi Gas Chemical Co., Ltd.

The average particle size of the inorganic peroxide is preferably 200 to 1000 μm, more preferably 300 to 800 μm. In order to satisfy both solubility and stability, the particle size of 125 μm or less and the particle of 1000 μm or more are 10% by mass. The following is preferable. Here, the average particle diameter can be confirmed by a method of obtaining a particle size distribution using a sieve and calculating from the particle size distribution.
Although the compounding quantity of (B) component in this invention is not restrict | limited in particular, If it is a bleaching composition, 20-90 mass% is preferable in a composition, More preferably, it is 25-90 mass%, More preferably, it is 30-90 mass%. Even if it exceeds the above range, the bleaching effect may not be enhanced against stain stains on clothing or yellowing stains on clothing that has been worn for a long time, and if less than the above range, sufficient bleaching effect against stubborn stains May not be obtained. If it is a bleaching detergent composition, 1 mass% or more and less than 20 mass% is preferable in a composition, More preferably, it is 2 mass% or more and less than 20 mass%. If the above range is exceeded, the bleaching effect against mild stains and the yellowing prevention effect of clothing may not be increased any more, and at the same time sufficient surfactant content cannot be secured and sufficient cleaning effect cannot be obtained There is. Moreover, if it is less than the said range, a bleaching effect may not be enough as a bleaching detergent composition.

(C) component (C) component of this invention is a bleaching catalyst. The bleaching catalyst acts catalytically in the bleaching solution and can continue to develop the bleaching effect as long as peroxide is present.
(C) The bleaching catalyst is composed of a transition metal atom such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum, and a ligand, such as a nitrogen atom or an oxygen atom. As the transition metal contained, cobalt, manganese and the like are preferable, and manganese is particularly preferable.
In this case, there is an arbitrary counter ion that balances with the stoichiometric charge generated by the combination of the transition metal atom and the ligand. In this case, preferred counter ions are chloride ion and ammonium ion.
As preferred ligands in the present invention, JP 2000-144188 A, JP 2000-54256 A, JP 2000-34497 A, JP 2000-508011, JP 2000-500518 A, JP-A-11-57488, JP-A-11-106790, JP-A-11-171893, JP-A-11-342341, JP-A-11-507689, JP-A-11-515049, JP-A-11-507923, JP-A-9-194886, JP-A-8-231987, JP-A-8-0667687, JP-A-8-503247, JP-B-7-065074, Japanese Patent Publication No. 7-068558, Japanese Patent Laid-Open No. 5-17485, International Publication No. 94/11479 Pamphlet And ligands disclosed in International Publication No. 93/15175 pamphlet, Japanese translations of PCT publication No. 2002-530281, Japanese translations of PCT publication No. 2002-538268, Japanese translations of PCT publication No. 2000-515194, and JP-A-2002-294290. More specific ligands include carboxylate-containing amines, 1,4,7-trimethyl-1,4,7-triazacyclononane and similar compounds, porphine and porphyrin , Phthalocyanine and water-soluble or water-dispersible derivatives having a skeleton thereof, 2,2′-dipyridyl derivative, 1,10-phenanthroline derivative, amine, tris (salicylideneiminoethyl) amine, N, N′-ethylenebis (4-hydroxysalicylideneiminate), N, N′-bis (salicylidene) ethylenedia 13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11-benzotetraazacyclotride Syn, 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6,6,2] hexadecane, 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6,6, 2] Hexadecane, bis (salicylideneiminoethyl) amine, bis (salicylideneiminoethyl) methylamine and the like.

  Specific bleach catalysts include carboxylate-containing cobaltamine, tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphorus. Acid salt, porphine or porphine derivative manganese complex, porphyrin or porphyrin derivative manganese complex, phthalocyanine or phthalocyanine derivative manganese complex, 2,2′-dipyridyl derivative manganese complex, 1,10-phenanthroline derivative manganese complex, cobalt amine, (tris (sali Tylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, N, N′-bis (salicylidene) ethylenediamine, 5,12-dimethyl- 1,5,8,12-te Laazabicyclo [6,6,2] hexadecane manganese (II) chloride, [13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H -1,4,8,11-benzotetraazacyclotridecine] -iron complex and the like. In the present invention, a more preferable bleach activation catalyst is tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphoric acid. Salt, (tris (salicylideniminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, (bis (salicylideniminoethyl) amine) -Manganese complexes, (bis (salicylideneiminoethyl) methylamine) -manganese complexes, N, N'-bis (salicylidene) ethylenediamine, etc., preferably from the viewpoint of bleaching power and clothing damage and fading (Salicylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate) ) - it is a manganese complex.

In the present invention, the preferred molar ratio of the transition metal atom and the ligand in the bleaching catalyst (C) in the present invention is 1: 1 to 1: 4. If the proportion of the ligand is smaller than this ratio, a complex is formed. Hydrogen peroxide is decomposed by transition metal atoms that are not formed, and the bleaching effect may be reduced. On the other hand, even if the ratio of the ligand is larger than this ratio, the bleaching effect is not further increased, which may be uneconomical.
In the present invention, the preferable content of the component (C) in the bleaching composition and the bleaching detergent composition depends on the amount of the (B) peroxide, and is expressed as a mass ratio of (B) :( C). = 300: 1 to 3: 1 is preferable, and 100: 1 to 6: 1 is more preferable. Usually, it is 0.001-1 mass%, 0.01-0.5 mass% is more preferable in a bleaching agent composition, and 0.005-0.5 mass% is more preferable in a bleaching detergent composition. Even if it exceeds the above range, the bleaching effect may not be enhanced any more, and at the same time, it may be difficult to suppress the damage and fading of clothing. Moreover, if it is less than the said range, sufficient bleaching effect may not be acquired.
In the present invention, the component (C) is granulated and molded using the granulation method of the component (D) or the method described in PCT / JP03 / 05700, etc., so that storage stability, clothing damage, fading, etc. Is preferable.
In the present invention, when the component (C) is used in the form of a granulated product or molded product, the content in the granulated product or molded product is preferably 1 to 20% by mass, more preferably 1 to 10% by mass. The preferable content of the granulated product or molded product in the bleaching composition and the bleaching detergent composition is 0.001 to 10% by mass, and in the bleaching composition, 0.1 to 10% by mass is more preferable. In a cleaning composition, 0.001-5 mass% is more preferable.

(D) component (D) component of this invention is a bleaching activator. Specifically, an organic peracid precursor can be used, and the precursor is a compound that generates an organic peracid by a peroxide such as hydrogen peroxide. In order to express the bleaching effect stoichiometrically, it is necessary to blend it at a high concentration, unlike the (C) bleaching catalyst which acts catalytically.
Specific examples of bleach activators include tetraacetylethylenediamine, pentaacetylglucose;
_{RCOO-C 6 H 4 -COOM (} I) ( wherein, R represents a straight or branched chain alkyl group or alkenyl group having 9 to 11 carbon atoms, M is an alkali metal, such as hydrogen or sodium, potassium, Bleaching activators represented by formulas such as sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, decanoyloxybenzene Sodium sulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate;
_{RCOO-C 6 H 4 -SO 3} M (II) ( wherein, R represents an alkyl group or alkenyl group having 9 to 11 carbon atoms linear or branched, M represents an alkali such as hydrogen or sodium, potassium Bleaching activators represented by formulas such as octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undeca Noyloxybenzoic acid, dodecanoyloxybenzoic acid;
Examples include octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene, and dodecanoyloxybenzene.
Moreover, the compound represented by the following general formula (1), (2) is also mentioned.

(In the formula, R ¹ is an alkyl group having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3 carbon atoms which may be separated by an ester group, an amide group or an ether group, and R ⁶ is an ester. R ² , R ³ , R ⁴ , R ⁴ , R ³ , R ⁴ , R ⁴ , R ³ , R ⁴ , R ⁴ , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group, and X ⁻ is an anion, preferably a halogen atom. An ion, a sulfate ion, a fatty acid ion, or an alkyl sulfate ion having 1 to 3 carbon atoms.)
In addition, the organic peracid produced from the bleach activator is sterilizing in laundry systems and has the effect of reducing the number of living microorganisms remaining in clothing (Yukitaka Miyamae, Satoshi Matsunaga, Seiichi Tobe, Takahashi) Kenji, Haruo Yoshimura, Teruhisa Uzuki, Abstracts of the 28th Symposium on Cleaning, p.157-165 (1996)). From the viewpoint of sterilizing power, a bleach activator that generates a C8 to C12 organic peracid is particularly preferable. Specifically, the bleach activator represented by the above (I) or (II) is preferable. Specific examples of these bleach activators include decanoyloxybenzoic acid, sodium dodecanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, and the like. Among them, 4-decanoyloxybenzoate is preferred in terms of bleaching effect. Acid, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are more preferable.

In the present invention, the (D) bleach activator is preferably blended as a granulated product or molded product from the viewpoint of storage stability during storage. The content of the bleach activator in the granulated product or molded product is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the content is outside this range, the effect of granulation may not be sufficiently obtained.
These are preferably made into a granulated product or a molded product using a binder compound selected from polyethylene glycol, a saturated fatty acid having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 and salts thereof. The polyethylene glycol is preferably polyethylene glycol 1000 to 20000 (average molecular weight 500 to 25000), more preferably an average molecular weight 2600 to 9300, particularly preferably an average molecular weight 5000 to 9300. In addition, the saturated fatty acid having 12 to 20 carbon atoms is preferably a saturated fatty acid having 14 to 20 carbon atoms, and more preferably 14 to 18 carbon atoms. In addition, the average molecular weight of the polyethylene glycol in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description. The weight average molecular weight of polyacrylic acid and its salt is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance. Such a binder substance is preferably used in the granulated product in an amount of 0.5 to 30% by mass, more preferably 1 to 20% by mass, and more preferably 5 to 20% by mass.

  In addition, the granulated product may contain polyoxyalkylene alkyl ether, olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt or polyoxyethylene alkyl to improve the solubility of the bleach activator in the washing bath. It is preferably used in combination with a surfactant such as an ether sulfate ester salt or a mixture thereof, and the content in the granulated product is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5%. -30 mass%. As polyoxyalkylene alkyl ether, the alkyl group preferably has 10 to 15 carbon atoms, and is preferably an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). The average added mole number is preferably 4 to 30, more preferably 5 to 15 in total in any case of EO, PO, or a mixture of EO and PO, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2. The olefin sulfonate is preferably a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms. The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group. Further, as the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as sodium salt is preferable, and sodium lauryl sulfate ester or myristyl sulfate ester sodium is particularly preferable. Moreover, as a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is favorable. Here, the average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is represented by POE) is 1 to 10, preferably 1 to 5, and particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ), Sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) is good.

In the present invention, the granulated product of the bleach activator can be produced by any method. In addition, a preferable result can be obtained by adding the binder substance after being melted in advance. The binder material is added after being melted at 40 to 100 ° C, preferably 50 to 100 ° C, more preferably 50 to 90 ° C. These are agitated and mixed until uniform, and then formulated with a normal granulator. Extrusion granulation can be mentioned as a preferable granulation method, and it is preferable to make a granulated product having an average particle size of 500 to 5000 μm, preferably 500 to 3000 μm. As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method.
Here, it is known that the bleach activator causes hydrolysis during storage due to the presence of alkali components and moisture in the bleach or bleach detergent, and loses the bleaching and sterilizing effects. Therefore, in the present invention, in order to prevent such decomposition, the bleach activator is mixed with a film-forming polymer, zeolite, etc. in addition to the binder and surfactant, and blended as a granulated product. Is more preferable.
The blending ratio of the granulated product containing the bleach activator in the bleaching agent composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass in the bleaching detergent composition (D ) The content of the component is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass. If the above range is exceeded, the bleaching effect may not increase any more, and if it is less than the above range, a sufficient bleaching effect may not be obtained.

In addition to the above essential components, the bleaching detergent composition of the present invention uses the following various components that are usually used for washing or blended in the bleaching composition within a range that does not interfere with the effects of the present invention. be able to.
<1> Examples of builders include inorganic and organic builders. Examples of the inorganic builder include, for example, alkaline salts such as sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate, neutral salts such as sodium sulfate, Phosphate such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc., general formula:
_{x1 (M 2 O) · Al} 2 O 2 · y1 (SiO 2) · w1 (H 2 O)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x1, y1 and w1 represent the number of moles of each component. In general, x1 is a number of 0.7 to 1.5, and y1 is 0.00. A crystalline aluminosilicate represented by a number of 8 to 6, w1 represents an arbitrary positive number, and a general formula:
_{x2 (M 2 O) · Al} 2 O 3 · y2 (SiO 2) · w2 (H 2 O)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x2, y2 and w2 represent the number of moles of each component. In general, x2 is a number of 0.7 to 1.2, and y2 is 1. An amorphous aluminosilicate represented by the number of 6 to 2.8, w2 represents 0 or any positive number, and a general formula:
_{x3 (N 2 O) · Al} 2 O 3 · y3 (SiO 2) · z3 (P 2 O 5) · w3 (H 2 O)
(In the formula, M represents an alkali metal atom such as sodium or potassium, x3, y3, Z3 and w3 represent the number of moles of each component. In general, x3 is a number of 0.2 to 1.1, and y3 is A number of 0.2 to 4.0, z3 is 0.001 to 0.8, and w3 is 0 or any positive number)
Amorphous aluminosilicates represented by Among the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, and sodium aluminosilicate are preferable.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxy Hydroxyaminocarboxylates such as iminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid , Benzopolycarboxylates, cyclocarboxylates such as cyclopentanetetracarboxylates; ether carboxylic acids such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate Salt: Polyacrylic acid (salt), acrylic acid-allyl alcohol copolymer (salt), water-soluble acrylic acid-maleic acid copolymer (salt), hydroxyacrylic acid polymer (salt), polysaccharide-acrylic acid copolymer Acrylic acid polymers and copolymers such as polymers, or salts thereof; polymers or copolymers of maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, and the like; Or salts thereof; polysaccharide oxides such as starch, cellulose, amylose, and pectin; polysaccharides such as carboxymethyl cellulose; non-dissociating polymer compounds such as polyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone. Among these organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, and water-soluble acrylic acid-maleic acid copolymer salt are preferable. The said builder is normally used individually or in mixture of 2 or more types. The amount of the builder is preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass in the detergent composition in order to impart sufficient detergency.

<2> As surfactants, examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. These may be used alone or in combination of two or more. They can be used in combination.
From the viewpoint of beverage stain stain removal performance, an anionic surfactant and a nonionic surfactant are preferred, and a combination of an anionic surfactant and a nonionic surfactant is more preferred. When an anionic surfactant and a nonionic surfactant are used in combination, the mass ratio of the anionic surfactant to the nonionic surfactant (anionic surfactant / nonionic surfactant) is 0.1 to 10. Preferably, 0.2 to 8 is more preferable, and 0.3 to 7 is more preferable.

1. Examples of anionic surfactants include the following.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.

(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) C8-20 saturated or unsaturated α-sulfo fatty acid salt or methyl, ethyl or propyl ester thereof (α-SF or MES).
(10) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) A higher fatty acid salt (soap) having 10 to 20 carbon atoms.
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.
Examples of the anionic surfactant include alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt) and alkali metal salts of AOS, α-SF, AS, AES (for example, sodium or potassium salt). Etc.), alkali metal salts of higher fatty acids (for example, sodium or potassium salts) and the like.

The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used. Examples of nonionic surfactants include the following.
(1) An average of 3 to 30 moles, preferably 4 to 20 moles, more preferably 5 to 17 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (3) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ⁹ CO (OA) _n OR ¹⁰ (3)
(In the formula, R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents an alkylene having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. Represents an oxide addition unit, and n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R ¹⁰ may have a substituent of 1 to 3 carbon atoms. Good lower alkyl group.)

(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite oleate.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
(9) Fatty acid alkanolamide.
(10) Polyoxyethylene alkylamine.
(11) Alkyl glycoside (12) Alkylamine oxide

Among the nonionic surfactants described above, the nonionic surfactant (1) described above is preferable, and an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 10 to 16 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether is preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 40 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, A fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester is preferably used. When a polyoxyalkylene alkyl ether is used, the polyoxyalkylene alkyl ether preferably has a sharp addition mole distribution of alkylene oxide (average addition mole number ± 2 is 80% by mass or more in terms of ± 2) from the standpoint of aroma of cleaning performance. . These nonionic surfactants can be used alone or in combination of two or more.
The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The melting point in the present invention is a value measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test methods”.

The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used. Examples of the cationic surfactant include the following.
(1) Di long chain alkyl dishort chain alkyl type quaternary ammonium salt (2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt (3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt The chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and the short chain alkyl is an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and a benzyl group having 2 to 4 carbon atoms, preferably 2-3 carbon atoms. A hydroxyalkyl group or a polyoxyalkylene group.)
The amphoteric surfactant is not particularly limited as long as it is conventionally used in detergents, and various amphoteric surfactants can be used.
In addition, this invention is not limited to the said surfactant, These can be used combining 1 type or 2 types or more suitably.

The content of the surfactant contained in the bleaching detergent composition is preferably 3 to 50% by mass, more preferably 15 to 40% by mass in the bleaching detergent composition from the viewpoint of imparting sufficient cleaning performance. More preferably, it is 15 to 35% by mass. Further, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 95% by mass or more of the total amount of the surfactant.
In the case of a bleaching composition, it is further washed by bleaching for the purpose of improving the solubility of hydrophobic components (fragrances, etc.) in the bleaching composition as well as in the granulated or molded product and improving the permeability to clothing. The surfactant used can be mix | blended with an agent composition. The content is preferably from 0.1 to 15% by mass, more preferably from 0.2 to 10% by mass.

<3> Examples of optical brighteners include bis (triazinylamino) stilbene disulfonic acid derivatives and bis (sulfostyryl) biphenyl salts.
<4> Examples of surface modifiers include finely divided calcium carbonate, finely divided zeolite, granular zeolite, and polyethylene glycol.
<5> Known as a recontamination inhibitor, cellulose derivatives such as carboxymethylcellulose (CMC), hydroxypropylmethylcellulose (HPMC), hydroxybutylmethylcellulose (HBMC), polyvinylpyrrolidone (PVP) and its derivatives, and soil release polymer (SRP) Among them, HPMC and SRP are preferable because of their high anti-recontamination effect, and 0.1 to 5% by mass is preferably incorporated in the bleaching composition of the present invention. Preferably, 0.5 to 3% is blended.
<6> As the porous oil absorbent, amorphous anhydrous silicic acid, calcium silicate, and the like.
<7> Examples of the flexibility-imparting agent include cationic surfactants such as dialkyl quaternary ammonium salts, clay minerals such as smectite, and the like.
<8> Silicone oil as an antifoaming agent.
<9> Fragrance <10> Colorants such as water-soluble dyes and pigments

<11> Other Enzymes Enzymes other than amylase that can be used as an essential component in the present invention can be used as they are as commercially available enzyme particles that are currently used in granular laundry detergents. Enzymes (which are enzymes that inherently perform enzyme action during the washing process) can be classified from the reactivity of the enzyme, such as hydrolases, oxidoreductases, lyases, transferases, and isomerases. However, any can be applied to the present invention. Particularly preferred are protease, esterase, lipase, nuclease, cellulase and pectinase.

Specific examples of the protease include savinase, alcalase, evalase, cannase, esperase (above, manufactured by Novozymes), API21 (produced by Showa Denko KK), and maxatase. (Maxtaze), Maxacal, Purefect, Purafect, Maxapem (manufactured by Genencor Corp.), KAP (manufactured by Kao Corporation), Protease K-14 and K- described in JP-A-5-25492 16 etc. can be mentioned. Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase. Specific examples of the lipase include commercially available lipases such as lipolase, lipolase ultra, lipex (manufactured by Novozymes), and liposome (manufactured by Showa Denko KK). Examples of the cellulase include commercially available cellzymes, carezymes (manufactured by Novozymes), KAC500 (manufactured by Kao Corporation), and cellulase according to claim 4 of JP-A 63-264699. These enzymes can be used alone or in combination of two or more. The enzyme is preferably granulated as a separate stable particle and used in a dry blended state with a detergent dough (particle). As a method for granulating the enzyme-containing particle, JP-A-53-6484 is disclosed. JP-A-60-262900, JP-A-62-257990, JP-A-1-112983, JP-T-3-503775, JP-A-4-503369, JP-A-2000-178593. And the method described in the Japanese Patent Publication. The average particle size of the enzyme-containing particles is preferably 200 to 1,000 μm, more preferably 300 to 700 μm, from the viewpoints of solubility and storage stability.
Components described in PCT / JP03 / 05700 other than the optional components (1) to (11) can also be suitably used in the present invention.

Preferable formulation examples of the composition of the present invention include the following:
(A) Amylase-containing granulated product having an amylase relative activity calculated by the above formula (2) of 120% or more: 0.1 to 5% by mass,
(B) Sodium percarbonate coated with or not coated with a coating agent such as boric acid or sodium silicate: 1 to 90% by mass,
(C) (Tris (salicylideniminoethyl) amine) -manganese complex, N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex and bis (salicylideniminoethyl) amine)- Any one type of bleaching catalyst-containing granule selected from the group consisting of manganese complexes: 0.001 to 10% by mass, and (D) 4-decanoyloxybenzoic acid, sodium 4-dodecanoyloxybenzenesulfonate, and A granulated product containing a bleach activator selected from the group consisting of sodium 4-decanoyloxybenzenesulfonate in an amount of 30 to 95% by mass,
A bleaching composition comprising:
Furthermore, it is particularly preferable to contain 0.1 to 3% by mass of protease and 0.1 to 3% by mass of lipase.

The bleaching composition of the present invention is not particularly limited in its preparation method. For example, if it is used as a high bulk density detergent, the high bulk density detergent particles are prepared according to a conventional method, and the detergent particles Can be prepared by mixing a granulated product of a bleaching inorganic peroxide, a bleach activator and a bleach catalyst.
The bulk density of the composition of the present invention is 0.6 g / mL or more, preferably 0.6 to 1.2 g / mL, and particularly preferably 0.7 to 1.0 g / mL.
When the bleaching composition of the present invention is a high bulk density granular bleaching detergent composition, the average particle size is 200 to 1000 μm, preferably 250 to 700 μm, more preferably 300 to 300 from the viewpoint of solubility and stability. The thickness is preferably 600 μm.
The bleaching composition of the present invention is suitably used as a washing agent for clothing and a bleaching agent for clothing, and the method of use thereof is not particularly limited, and can be used in a conventional manner.
The bleaching composition of the present invention can also be used as a bleaching agent. The usage method is not particularly limited, and can be used by a conventional method.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.
1. (A) Measurement of amylase relative activity (i) Preparation of test cloth 0.15 mL of red wine (Suntory Reserve) was dropped on an oil-based cooperative cloth (5 × 5 cm, obtained from the Laundry Science Association) and indoors (25 ° C. , 60% humidity) for 12 hours was used as a test cloth.
(Ii) Preparation of aqueous solution containing amylase Steinzyme (registered trademark) 12T (manufactured by Novozymes), Termamyl (registered trademark) 120T (manufactured by Novozymes), and Duramil (registered trademark) 120T (manufactured by Novozymes) were prepared as amylases. . A 25 ° C. solution in which each amylase was diluted 1000 times with 3 degree hard water (German hardness) was prepared. On the other hand, 25 mL of 3 ° C. hard water (German hardness) containing 150 ppm each of sodium carbonate and sodium bicarbonate was prepared. In addition, pH of the obtained aqueous solution was 10 (25 degreeC). Here, a 1000-fold diluted solution of amylase prepared in advance was added so that the weight of enzyme protein was 0.15 mg, and an amylase-containing aqueous solution was obtained.
As a control aqueous solution, 25 ° C., pH 10, 3 degree hard water (German hardness) containing sodium carbonate and sodium hydrogen carbonate in amounts of 150 ppm each were used.

(Iii) Amylase activity test Two test cloths prepared in step (i) were immersed in the amylase-containing aqueous solution prepared in step (ii) and allowed to stand for 30 minutes. During the standing, the liquid temperature was kept at 25 ° C. After leaving for 30 minutes, the two test cloths were taken out, immersed in 2 L of ion exchange water, and rinsed by stirring for 1 minute by hand. After rinsing twice in the same procedure, the amylase activity test was performed by drying in a light-shielded room (25 ° C., humidity 60%) for 12 hours.
A control test fabric was tested in a similar procedure except that a control aqueous solution was used.
(Iv) Measurement of amylase activity and relative activity The amylase activity was measured by measuring the reflectance (WB value) of the test cloth before and after the test using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Σ2000, using a 460 nm cut filter). The amylase activity was calculated by substituting the obtained reflectance into the above formula (1), and further the amylase relative activity was calculated from the above formula (2). The results obtained are shown in Table A.
Further, an amount of hydrogen peroxide concentration of 50 ppm was added to each amylase-containing aqueous solution and each control aqueous solution, and amylase activity and amylase relative activity were determined in the same procedure. The results are also shown in Table A.
The numerical values shown in Table A are average values of three experiments, and the measurement error is ± 10%.

2. (C) Bleaching catalyst synthesis method Catalyst A: (Synthesis of tris (salicylideniminoethyl) amine) -manganese complex Tris (2-aminoethyl) amine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (Tokyo Chemical Industry Co., Ltd. reagent), manganese chloride tetrahydrate (Kanto Chemical Co., Ltd. reagent), methanol (Kanto Chemical Co., Ltd. reagent), ethanol (Kansu Chemical Industry Co., Ltd. reagent) The synthesis was carried out by the following method.
38.7 g (0.333 mol) of tris (2-aminoethyl) amine was placed in a reaction vessel, dissolved in 300 mL of methanol, and cooled to 0 ° C. A solution obtained by dissolving 121.9 g (0.998 mol) of salicylaldehyde in 100 mL of methanol was added dropwise thereto over 1 hour. After completion of dropping, the mixture was further stirred at 0 ° C. for 1 hour. After completion of stirring, the mixture was allowed to stand at 0 ° C. for 3 hours, and the precipitated yellow crystals were filtered using a Kiriyama funnel. The obtained crystals were recrystallized with 500 mL of ethanol and purified to obtain 143 g of tris (salicylideniminoethyl) amine crystals.
1.0 g (0.002 mol) of the tris (salicylideniminoethyl) amine crystals obtained above was dissolved in 100 mL of ethanol, and 0.43 g (0.002 mol) of manganese chloride tetrahydrate was added to this solution. Added at room temperature. After concentrating ethanol to about 50 mL under reduced pressure, the mixture was allowed to stand at 5 ° C. for 24 hours. The precipitated dark green crystals were separated by filtration to obtain 1.1 g of crystals of (tris (salicylideniminoethyl) amine) -manganese complex (catalyst 2).
It is shown in the following formula.

Catalyst B: Synthesis of (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex As materials, ethylenediamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dihydroxybenzaldehyde (Kanto Chemical) Reagents), Manganese chloride tetrahydrate (Reagents manufactured by Kanto Chemical Co., Inc.), Methanol (Reagents manufactured by Kanto Chemical Co., Ltd.), Ethanol (Reagents manufactured by Gansu Chemical Industry Co., Ltd.) Synthesis was carried out by the method.
30.1 g (0.501 mol) of ethylenediamine was placed in a reaction vessel, dissolved in 300 mL of methanol, and cooled to 0 ° C. A solution prepared by dissolving 138.1 g (1.000 mol) of 2,4-dihydroxybenzaldehyde in 100 mL of methanol was added dropwise thereto over 1 hour. After completion of dropping, the mixture was further stirred at 0 ° C. for 1 hour. After completion of stirring, the mixture was allowed to stand at 0 ° C. for 3 hours, and the precipitated yellow crystals were filtered using a Kiriyama funnel. The obtained crystals were recrystallized with 500 mL of ethanol and purified to obtain 135 g of N, N′-ethylenebis (4-hydroxysalicylideneiminate) crystals.
1.0 g (0.003 mol) of the crystals of N, N′-ethylenebis (4-hydroxysalicylideneiminate) obtained above were dissolved in 100 mL of ethanol, and manganese chloride tetrahydrate was added to this solution in an amount of 0. 66 g (0.003 mol) was added at room temperature. After concentrating ethanol to about 50 mL under reduced pressure, the mixture was allowed to stand at 5 ° C. for 24 hours. The precipitated brown crystals were filtered off to obtain 1.0 g of crystals of (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex (catalyst 3).
It is shown in the following formula.

Catalyst C: Synthesis of (bis (salicylideneiminoethyl) amine) -manganese complex Diethylenetriamine (reagent made by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (reagent made by Tokyo Chemical Industry Co., Ltd.), manganese chloride / 4 water The synthesis was performed by the following method using a Japanese product (a reagent manufactured by Kanto Chemical Co., Inc.) and methanol (a reagent manufactured by Kanto Chemical Co., Ltd.).
50 ml of methanol solution of 1.68 g (16.28 mmol) of diethylenetriamine and 50 ml of methanol solution of 3.99 g (32.67 mmol) of salicylaldehyde were mixed and stirred at room temperature for 10 minutes. Subsequently, the solvent was distilled off under reduced pressure to obtain a yellow liquid of bis (salicylideniminoethyl) amine. (Yield 100%)
1.04 g (3.2 mmol) of the bis (salicylideniminoethyl) amine crystals obtained above and 0.63 g (3.2 mmol) of manganese chloride tetrahydrate were dissolved in 20 ml of methanol and dissolved at room temperature. Left for days. The produced crystals were collected by filtration, washed with methanol, and dried to obtain 0.54 g of crystals of (bis (salicylideneiminoethyl) amine) -manganese complex. It is shown in the following formula.

3. (C) Preparation method of granulated product containing bleaching catalyst (i) Preparation method of metal catalyst granulated product A As a metal catalyst, 10 parts by mass of (tris (salicylideneiminoethyl) amine) -manganese complex, PEG [polyethylene Glycol # 6000M (manufactured by Lion Co., Ltd.)] 70 parts by mass, powdered cellulose (Arbocel FD600 / 30 (manufactured by Rettenmeier)), carbon 14 α-olefin sodium sulfonate powder product (Lipolane PJ-400) (Lion Co., Ltd.)) Noodle-shaped noodles with a diameter of 0.8 mmφ were put into an Extrude Ohmics EM-6 model manufactured by Hosokawa Micron Co., Ltd. so as to be a total of 5000 g at a ratio of 10 parts by mass, and kneaded and extruded. An extruded product was obtained. This extruded product (60 ° C.) was introduced into a Fitzmill DKA-3 type manufactured by Hosokawa Micron Corporation and pulverized to obtain a metal catalyst granulated product A having an average particle size of about 500 μm.
(Ii) Preparation method of metal catalyst granulated product B A metal catalyst was prepared in the same manner as metal catalyst A except that (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex was used as the metal catalyst. Catalyst granulated product B was prepared.
(Iii) Preparation method of metal catalyst granulated product C A metal catalyst granulated product C was prepared in the same manner as the metal catalyst A except that (bis (salicylideneiminoethyl) amine) -manganese complex was used as the metal catalyst. did.

4). (D) Preparation method of granulated product containing bleach activator (i) Preparation method of bleach activator granulated product A 4-Decanoyloxybenzoic acid (manufactured by Mitsui Chemicals, Inc.) as a bleach activator 70 parts by mass, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)], 5 parts by mass of sodium α-olefin sulfonate powder having 14 carbon atoms (Lipolane PJ-400 (manufactured by Lion Corporation)) The mixture was put into an Extrude Ohmic EM-6 model manufactured by Hosokawa Micron Co., Ltd. so that the total amount was 5000 g, and kneaded and extruded to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 manufactured by Hosokawa Micron Co., and 5 parts by mass of A-type zeolite powder was supplied in the same manner as an auxiliary agent, and pulverized to give bleaching activity having an average particle size of about 700 μm. An agent granulated product A was obtained.
(Ii) Preparation method of bleach activator granulated product B Bleach activator granulated product in the same manner as bleach activator A except that sodium 4-dodecyloxybenzenesulfonate was used as the bleach activator. B was prepared.

5. Method for producing builder particles 85.5 parts by weight of sodium carbonate (granular ash manufactured by Asahi Glass Co., Ltd.) is provided in a blow shear mixer (Pacific Machinery Corporation) equipped with a bladed shovel and a shovel-wall clearance of 5 mm. Then, stirring was started at a spindle of 150 rpm (chopper rotation speed: 1015 rpm, blade tip speed (circumferential speed): 6.9 m / s). 10 seconds after the start of stirring, 7.5 parts by weight of sodium salt of acrylic acid / maleic acid copolymer (Nippon Shokubai Aquaric TL-400, 40% solid content aqueous solution) is a pressure nozzle (flat nozzle) with a spray angle of 115 degrees And spraying for 180 seconds to perform granulation / coating operation.
Subsequently, 7 parts by weight of lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees while continuing to stir the blow shear mixer. Stirring was continued for 30 seconds to obtain particles.
Next, the obtained particles are packed into a fluidized bed (Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is sent into the fluidized bed, The cooling operation was performed to obtain particles cooled to 20 ° C. The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state. The obtained particles were classified using a sieve having an opening of 2,000 μm to obtain builder particles having an average particle diameter of 350 μm and a bulk density of 1.14 g / mL passing through a sieve having an opening of 2,000 μm.

6). Method for preparing a bleaching composition
(i) Method for preparing bleach detergent composition (Part 1)
Among the bleaching detergent compositions shown in Table 1, Examples 1 to 5 and Comparative Example 7 were prepared by the following procedure.
A slurry for spray drying having a solid content of 40% by mass was prepared using each component excluding nonionic surfactant, part of zeolite, layered silicate, enzyme, fragrance, dye, sodium percarbonate, and metal catalyst granule. . The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C., reduced for 2 hours) is 3%, the bulk density is 0.35 g / mL, and the average particle size is 300 μm spray-dried particles were obtained. In addition, fine powder A-type zeolite (Silton B, Mizusawa Chemical) was used as the zeolite of the slurry for spray drying. This was put in a biaxial continuous kneader (Kurimoto Steel Works, KRC Kneader # 2 type) kept at 40 ° C. together with a part of the nonionic surfactant and water for water adjustment to obtain a kneaded product. Thereafter, this kneaded product was extruded and chopped into 1 to 2 cm square dice, and pulverized and granulated together with 3% by mass of granule A-type zeolite (average particle size 200 μm: manufactured by Cosmo). Using a crusher (Okada Seiko, speed mill ND-10 type), a screen with an opening diameter of 2 mm was used at a rotation speed of 1500 rpm. The obtained crushed granulated material was coated with 2% by mass of finely divided A-type zeolite (Silton B, Mizusawa Chemical) with a rolling drum, and after spraying a part of the nonionic surfactant (1% by mass), the average particle size Was adjusted to 500 μm.
In addition to this, sodium percarbonate, bleach activator granulated product, metal catalyst granulated product, enzyme and layered silicate are mixed with a rolling drum, and further, 20% aqueous pigment dispersion and flavor are added by spraying. A high bulk density granular bleach detergent composition was obtained. The resulting high bulk density granular bleaching detergent composition had a bulk density of 0.85 g / mL and an average particle size of 560 μm. About the high bulk density granular bleaching detergent composition, the bleaching performance with respect to the stain stain of red wine was evaluated according to the following evaluation method. The results are also shown in Table 1.

(ii) Preparation method of bleach detergent composition (part 2)
Among the detergent compositions shown in Table 1, Example 6 and Comparative Example 8 were prepared by the following procedure.
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. Sodium sulfate and fluorescent brightening agent were added thereto, and after stirring for 10 minutes, sodium carbonate was added, and then an acrylic acid polymer and hydroxypropylmethylcellulose (HPMC) were added. After further stirring for 10 minutes, sodium chloride and powdered zeolite A portion of was added. The mixture was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C., reduced for 2 hours) is 3%, the bulk density is 0.50 g / mL, and the average particle size is 250 μm spray-dried particles were obtained.
Next, a nonionic surfactant and an anionic surfactant were added under mixing at 80 ° C. to prepare a surfactant composition having a water content of 10% by mass.
Next, spray-dried particles were put into a Redige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the main shaft (150 rpm) and chopper (4000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. The surfactant composition was added to the mixture for 2 minutes, and then stirred for 5 minutes. Then, a layered silicate and a part (10% by mass) of the powdered zeolite were added to perform a surface coating treatment for 2 minutes. A detergent composition was obtained.
After mixing a part (2% by mass) of the powdered zeolite with this detergent composition with a V blender, an enzyme, a percarbonate, a metal catalyst granulated product and a bleach activator are mixed with a V blender, Further, a 20% aqueous dye dispersion and a fragrance were added by spraying to obtain a high bulk density granular bleaching detergent composition. The resulting high bulk density granular bleaching detergent composition had a bulk density of 0.75 g / mL and an average particle size of 300 μm. About the high bulk density granular bleaching detergent composition, the bleaching performance with respect to the stain stain of red wine was evaluated according to the following evaluation method. The results are also shown in Table 1.

(Iii) Preparation method of bleach composition The bleach composition shown in Table 2 was prepared by the following procedure. Each component excluding sodium percarbonate, metal catalyst granulated product, bleach activator granulated product, enzyme, fragrance, pigment, and surfactant was put into a Redige mixer M20 type (Matsuzaka Giken Co., Ltd.) Agitation of the main shaft (150 rpm) and chopper (1000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. A surfactant mixture previously heated to 80 ° C. and mixed therein was added for 2 minutes, and then stirred for 10 minutes, and a 20% aqueous pigment dispersion and a fragrance were added by spraying to obtain mixed granules.
This mixed granule was mixed with sodium percarbonate, metal catalyst granulated product, bleach activator granulated product and enzyme using a V blender to obtain a bleaching composition. The resulting bleaching composition had a bulk density of 0.80 g / mL and an average particle size of 600 μm. About the bleaching agent composition, the bleaching performance with respect to the stain stain of red wine was evaluated according to the following evaluation method. The results are also shown in Table 2.

7). Beverage stain stain removal performance evaluation (1) Creation of beverage stain stain 0.15 ml of red wine (Suntory Reserve) was dropped onto oily cooperative cloth (5 × 5 cm) and dried in a room (25 ° C., humidity 60%) for 12 hours. This was used as a test cloth.
(2) Evaluation of removal performance of bleach detergent composition The bleach detergent composition shown in Table 1 was added to the amylase-containing aqueous solution and control aqueous solution prepared in the same manner as described in (ii) so that the concentration of the bleach detergent composition was 0.05%.
Using Teg-O-meter of Testing Corp. in the United States as a cleaning tester, put the above three red wine stain test cloths and cleaning knitted cloth so that the total weight of the cloth is 30 g, and adjust the bath ratio to 30 times, 120 rpm, Washed for 10 minutes at 25 ° C. The water used was 3 ° DH, the amount of the washing liquid was 900 mL, and the rinse was washed with 900 mL of ion-exchanged water for 3 minutes. After rinsing, the red wine stain test cloth was dried and the reflectance was measured. The reflectance was measured with Σ2000 (Nippon Denshoku Industries Co., Ltd.) using a 460 nm cut filter. The obtained reflectance was substituted into the following formula (3) to calculate the beverage stain stain removal rate. The obtained results are also shown in Table 1.
In addition, as a result of evaluating the washing | cleaning property and recontamination property of the bleaching detergent composition of Examples 1-6 by the washing | cleaning test, the recontamination property of the bleaching detergent composition of Example 1 was favorable. It has also been confirmed from the recontamination evaluation with and without HPMC that the effect of suppressing this recontamination is due to the blending of HPMC.

(3) Bleaching performance evaluation of bleach composition Bleach the bleach composition shown in Table 2 together with the concentration of 0.05% by weight of the detergent composition shown in Comparative Example 7 in Table 1 on the amylase-containing aqueous solution and control aqueous solution prepared in the same manner as described in (ii). It was added so that the agent composition concentration would be 0.03%.
Using a Terg-O-meter as a washing tester in the United States of America, put the above three red wine stain test cloths and the washing knitted cloth so that the total weight of the cloth is 30 g, and adjust the bath ratio to 30 times to 30. I left it for a minute. After completion of soaking, washing was performed at 120 rpm and 25 ° C. for 10 minutes. The water used was 3 ° DH, the amount of the washing liquid was 900 mL, and the rinse was washed with 900 ml of ion-exchanged water for 3 minutes. After rinsing, the red wine test cloth was dried, and the bleaching performance of the bleaching composition was evaluated according to the same procedure as that for evaluating the removal performance of the bleaching detergent composition in 6. (2). The obtained results are also shown in Table 2.

The components used in the above examples are as follows.
(A) Component amylase: Steinzyme 12T (manufactured by Novozymes)
(B) Component percarbonate A: coated sodium percarbonate (SPC-D manufactured by Mitsubishi Gas Chemical Co., Inc.)
Percarbonate B: Sodium percarbonate (SPC-Z manufactured by Mitsubishi Gas Chemical Co., Inc.)
(C) Component metal catalyst granulated product A: metal catalyst granulated product obtained by the method for preparing metal catalyst granulated product A Metal catalyst granulated product B: obtained by the method for preparing metal catalyst granulated product B Metal catalyst granulated product Metal catalyst granulated product C: Metal catalyst granulated product (D) component bleach activator granulated product A obtained by the method for preparing metal catalyst granulated product C: Bleach activator Bleach activator granulated product obtained by the granulated product A preparation method Bleach activator granulated product B: Bleach activator granulated product obtained by the above bleach activator granulated product B preparation method

(Surfactant)
α-SF-Na: 14 carbon atoms: sodium salt of α-sulfo fatty acid methyl ester having carbon number 16 = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate, Methyl sulfate, hydrogen peroxide, water, etc.)
LAS-K: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (manufactured by Lion Corporation) LAS-H pure 96%) is neutralized with 48% aqueous potassium hydroxide during preparation ). The compounding quantity in Tables 1-3 shows the mass% as LAS-K.
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (96% pure LAS-H) manufactured by Lion Co., Ltd. is neutralized with 48% aqueous sodium hydroxide during preparation) . The compounding quantity in Tables 1-3 shows the mass% as LAS-Na.
AOS-K: Potassium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
Soap: Fatty acid sodium having an alkyl group having 12 to 18 carbon atoms (manufactured by Lion Corporation)
Nonionic surfactant A: ECOROL 26 (alcohol having an alkyl group of 12 to 16 carbon atoms manufactured by ECOGREEN) adduct with an average of 15 moles of ethylene oxide (pure content 90%)
Nonionic surfactant B: Diamond Dole 13 (manufactured by Mitsubishi Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide adduct and 85% of adducts with 3 to 7 moles of ethylene oxide added (pure 90%)

(Builders, etc.)
Sodium carbonate: Heavy sodium carbonate (Asahi Glass Co., Ltd., soda ash)
Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.)
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
Sodium chloride: Nissei Yaki salt C (manufactured by Nippon Salt Co., Ltd.)
Layered silicate: crystalline layered sodium silicate (SKS-6 manufactured by Clariant Tokuyama)
Sodium silicate: JIS No. 1 sodium silicate (manufactured by Nippon Chemical Co., Ltd.)
White carbon: Tokuseal (manufactured by Tokuyama)
Zeolite: Type A zeolite (Silton B manufactured by Mizusawa Chemical Co., Ltd.)
Acrylic acid-based polymer A: sodium salt of acrylic acid / maleic acid copolymer, trade name Socaran CP7 (BASF)
Acrylic acid polymer B: Sodium polyacrylate, trade name Socaran PA30 (BASF)
HPMC: hydroxypropyl methylcellulose, trade name Metroz 65SH-1500 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Fluorescent whitening agent: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) and Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) with a mass ratio of 8/2 Builder particles: International application number PCT / JP2004 / 005910 Surface-treated water-soluble inorganic compound particle protease A: sabinase 12T having the composition of Example a1 in [Table 1] prepared according to the method 1 (stir granulation 1) for producing surface-treated water-soluble inorganic compound particles of the described Examples and Comparative Examples (Novozymes)
Protease B: Everase 8T (Novozymes)
Lipase: Lipex 50T (manufactured by Novozymes)
Cellulase: Cellzyme 0.7T (manufactured by Novozymes)
Dye A: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue)
Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo)
Fragrance A: Fragrance composition A shown in JP-A-2002-146399, Tables 11-18
Fragrance B: Fragrance composition B shown in JP-A-2002-146399, Tables 11-18
Perfume C: Perfume composition C shown in JP-A-2002-146399, Tables 11-18
Perfume D: Perfume composition D shown in JP-A-2002-146399, Tables 11-18

Claims (11)

(A) A bleaching composition comprising an amylase having an amylase relative activity calculated according to the following formulas (1) and (2) of 120% or more.

  (A) The bleaching composition according to claim 1, wherein the relative activity of the amylase is 130% or more.   (A) The bleaching composition according to claim 1, wherein the amylase is Steinzyme (registered trademark).   The bleaching composition according to any one of claims 1 to 3, further comprising (B) a peroxide that releases hydrogen peroxide in water.   (B) The bleaching composition according to claim 4, wherein the peroxide is coated or uncoated sodium percarbonate.   The bleaching composition according to any one of claims 1 to 5, further comprising (C) a bleach catalyst or (D) a bleach activator.   (C) The bleaching catalyst comprises (tris (salicylideneiminoethyl) amine) -manganese complex, N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex and bis (salicylideneimino) The bleaching composition according to claim 6, which is any one selected from the group consisting of an ethyl) amine) -manganese complex.   Furthermore, bleaching composition of any one of Claims 1-7 containing protease and / or lipase. A method for removing beverage stain stains,
(I) preparing an amylase having an amylase relative activity of 120% or more calculated according to the following formulas (1) and (2);

(Ii) adding the amylase prepared in step (i) to basic adjusted water to prepare a basic aqueous solution containing amylase; and (iii) containing the amylase obtained in step (ii) Treating a textile product having a beverage stain with a basic aqueous solution;
A method for removing stains from beverage stains.   10. The method according to claim 9, wherein in step (ii), (B) a peroxide that releases hydrogen peroxide in water is added to prepare a basic aqueous solution containing amylase.   11. The method according to claim 10, wherein in step (ii), (C) a bleach catalyst or (D) a bleach activator is further added to prepare a basic aqueous solution containing amylase.