JP2006143853A - Amylase-containing bleaching composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching detergent composition having high removing effect of spilled food even by ordinary washing. <P>SOLUTION: The bleaching composition contains (A) a peroxide releasing hydrogen peroxide in water, (B) a bleaching activation agent expressed by formula (I): RCOO-C<SB>6</SB>H<SB>4</SB>-COOM or formula (II): RCOO-C<SB>6</SB>H<SB>4</SB>-SO<SB>3</SB>M (R is a straight or branched-chain 9-11C alkyl or alkenyl; and M is hydrogen or a salt-forming cation), (C) a surfactant and (D) an amylase having a viscosity reducing percentage of ≥40% wherein the viscosity reducing percentage is defined by [(initial viscosity - viscosity after 60 min)/(initial viscosity)]×100(%). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a bleaching composition such as a bleaching agent and a bleaching detergent used for textiles such as clothing. Specifically, the present invention relates to a bleaching composition containing a specific amylase having a high effect of spilling dirt.

A detergent for clothing having a bleaching effect has been used favorably in recent years because it can effectively remove stains such as tea, coffee, fruit and blood simultaneously with the removal of lipid stains adhering 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. As the bleach activator, those of peracid precursors are typical, and among them, those using peracetic acid such as tetraacetylethylenediamine, acetoxybenzenesulfonate, tetraacetylglycoluril, and C8-C14 Some use long-chain peracids such as alkanoyloxybenzenesulfonic acid / salt or C10-C14 alkanoyloxybenzoic acid / salt (see, for example, Patent Documents 1 to 4). The peracetic acid type generates acetic acid odor as a base odor, so the long chain peracid type is suitable as a washing base for clothing.
On the other hand, a bleaching detergent composition combining a substance that releases hydrogen peroxide in water, a bleach activator with a specific structure, and amylase, which has an excellent effect on stains containing a large amount of starch such as curry, is proposed. (Patent Document 5), the bleaching time is as long as 1 hour, the washing solution concentration is as high as 0.5%, and the washing solution temperature is evaluated at a constant high temperature of 35 ° C. In the washing conditions (washing time: about 10 minutes, washing concentration: 0.05 to 0.1%, washing temperature: 10 to 25 ° C.), the effect is insufficient and normal washing Therefore, a bleaching detergent capable of exhibiting excellent bleaching performance has been desired.

JP 7-33295 A JP-A-8-92594 JP-A-9-176688 JP 2002-3889 A JP-A-10-95996

  In view of the above circumstances, an object of the present invention is to provide a bleaching detergent composition that is highly effective in removing spilled dirt even by ordinary washing.

As a result of intensive studies to solve the above problems, the present inventors have combined an inorganic peroxide that releases hydrogen peroxide in water with a specific bleach activator, a specific amylase, and a surfactant. The inventors have found that the above object can be achieved and have completed the present invention.
That is, this invention provides the bleaching composition characterized by containing the following components.
(A) a peroxide that releases hydrogen peroxide in water;
(B) a bleach activator represented by the following formula (I) or (II):
_{RCOO-C 6 H 4 -COOM (} I)
_{RCOO-C 6 H 4 -SO 3} M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 9 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation.)
(C) Surfactant and (D) Amylase whose viscosity reduction rate calculated by the following formula (1) is 40% or more.

  According to the present invention, a bleaching composition capable of effectively and simply removing spilled dirt is obtained. According to the present invention, the effect of removing odors derived from spilled dirt is also excellent.

As the peroxide that releases hydrogen peroxide in water as the component (A) of the present invention, a percarbonate or a perborate is preferable. Specific examples include sodium percarbonate and sodium perborate. As the percarbonate, a commercially available product can be used, and specific examples include sodium percarbonate sold by Mitsubishi Gas Chemical Co., Ltd. under the trade name SPC-Z.
In addition, when used in a detergent containing zeolite or containing a relatively large amount of water, for example 3% or more, sodium percarbonate coated with an inorganic or organic compound and stabilized may be used. preferable. Examples of the coating agent include boric acid or borate, amorphous silicate, magnesium salt, or water-insoluble organic compounds such as paraffin and wax. Boric acid and amorphous silicate are preferred. 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 size of 1250 μm or more are 10% by mass. The following is preferable. The amount of the inorganic peroxide is usually 1 to 90% by mass, more preferably 2 to 70% by mass, and still more preferably 3 to 60% by mass with respect to the entire composition. When using as a bleaching detergent composition, 1-20 mass% with respect to the whole composition, More preferably, 2-15 mass%, More preferably, 3-10 mass% is suitable. When used as a bleaching agent composition, 20 to 90% by mass, more preferably 25 to 70% by mass, and still more preferably 30 to 50% by mass with respect to the entire composition. In addition, in this specification, the measurement of the average particle diameter and bulk density of a particle shall be based on the measuring method as described in the Example mentioned later.

Examples of the bleach activator used as the component (B) of the present invention include compounds represented by the above formula (I) or (II).
In formulas (I) and (II), as the alkyl group and alkenyl group represented by R, both linear and branched groups can be used, but linear ones are preferred. R is preferably an alkyl group having 9 to 11 carbon atoms. M is a salt-forming cation that imparts water solubility to hydrogen or a bleach activator, and specific examples include alkali metals such as sodium and potassium, and amines such as ammonium and alkanolamine. Of these, alkali metals are particularly preferred. In the formula, the SO ₃ M group and the COOM group can be in the ortho, meta or para position, but the para position is preferred.
The blending amount of the bleach activator is usually 0.1 to 10%, more preferably 0.2 to 5%, still more preferably 0.3 to 3% with respect to the entire composition. When used as a bleaching detergent composition, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and still more preferably 0.3 to 3% by mass, based on the entire composition. . When used as a bleaching agent composition, 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 3% by mass with respect to the total composition. .

In the present invention, the bleach activator is preferably blended as a granulated product from the viewpoint of storage stability. For example, such a granulated product is obtained by heating and melting a solid binder substance such as polyethylene glycol having an average molecular weight of 1000 to 20000, preferably 4000 to 8000 at room temperature, and then bleaching activator, olefin sulfonate, and alkylbenzene. Manufactured by dispersing powders of surfactants such as sulfonates and alkyl sulfates, and extruding them to produce noodle-like bleach activator granules with a diameter of about 0.6 to 1 mm, followed by light pulverization can do. As the surfactant powder, an α-olefin sulfonate having an alkyl chain length of 14 is preferred. The bleaching activator, the binder substance and the surfactant can all be put into an extruder and kneaded and extruded.
The blending amount of the bleach activator in the granulated product is preferably 30 to 90% by mass, more preferably 50 to 80% by mass. If the blending amount is outside this range, the effect of granulation may not be sufficiently obtained.
The compounding amount of the binder material is 0.5 to 30% by mass in the granulated product, preferably 1 to 25% by mass, more preferably 5 to 20% by mass, and the compounding amount of the surfactant powder is Preferably it is 0-50 mass% in a granulated material, More preferably, it is 3-40 mass%, Most preferably, it is 5-30 mass%.
The blending amount of the bleach activator granulated product is 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, further preferably 0.3 to 5% by mass with respect to the total amount of the bleach detergent composition. is there.

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. Moreover, the weight average molecular weight of the water-soluble polymer compound described later is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.
Examples of the surfactant used as the component (C) of the present invention include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants. These can be used individually by 1 type or in combination of 2 or more types as appropriate.
From the viewpoint of cleaning 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.

The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms
(2) C10-20 alkyl sulfate (AS) or alkenyl sulfate (3) C10-20 α-olefin sulfonate (AOS)
(4) Alkanesulfonate having 10 to 20 carbon atoms (5) Ethylene oxide or propylene having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Alkyl ether sulfate (AES) or alkenyl ether sulfate to which oxide, butylene oxide or a mixture thereof is added (6) having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole Alkyl ether carboxylate or alkenyl ether carboxylate to which ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a number of 10 moles or less is added (7) Alkyl polycarboxylic acid such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms Monohydric alcohol ether sulfate (8) charcoal Higher fatty acid salt of several 10 to 20 (9) Saturated or unsaturated α-sulfo fatty acid (α-SF) salt of 8 to 20 carbon atoms or methyl, ethyl or propyl ester thereof As anionic surfactant, linear alkylbenzene Alkali metal salt of sulfonic acid (LAS) (for example, sodium or potassium salt), alkali metal salt of AOS, α-SF, AES (for example, sodium or potassium salt), alkali metal salt of higher fatty acid (for example, sodium) Or a potassium salt).

Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms 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 (I) in which alkylene oxide is added between ester bonds of long chain fatty acid alkyl ester
R1CO (OA) nOR2 (I)
(In the formula, R 1 CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably 2 to 3 carbon atoms. N represents the average number of moles of alkylene oxide added and is generally a number of 3 to 30, preferably 5 to 20. R2 is a lower group which may have a substituent of 1 to 3 carbon atoms ( C1-4 represents an alkyl group.)
(4) Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbite fatty acid ester (6) Polyoxyethylene fatty acid ester (7) Polyoxyethylene hydrogenated castor oil (8) Glycerin fatty acid ester

Among the above nonionic surfactants, the above-described nonionic surfactant (1) 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 12 to 16 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether is preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° 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. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate.
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 melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.

The compounding amount of the anionic surfactant as the component (C) is usually 1 to 30% (mass%, the same applies hereinafter), more preferably 3 to 22%, and further preferably 5 to 18% with respect to the entire composition. Is preferred. When used as a bleaching detergent composition, 1 to 30% by weight, more preferably 5 to 20% by weight, and still more preferably 8 to 15% by weight is suitable for the whole composition. When used as a bleaching agent composition, 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 10% by mass with respect to the total composition.
The blending amount of the nonionic surfactant as the component (C) is usually 1 to 30%, more preferably 3 to 20%, still more preferably 5 to 20% with respect to the entire composition. When used as a bleaching detergent composition, it is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 12% by mass, based on the entire composition. When used as a bleaching agent composition, 1 to 10% by mass, more preferably 2 to 9% by mass, and still more preferably 3 to 8% by mass with respect to the total composition.
The content ratio of the anionic surfactant and the nonionic surfactant in the component (C) is such that the mass ratio of the anionic surfactant / nonionic surfactant is 0.8 to 3 (0.8 ≦ (anionic interface). The activator / nonionic surfactant)) ≦ 3) is preferable, and is preferably 0.8 or more and 2.8 or less, more preferably 0.9 or more and 2.5 or less. If the ratio of the anionic surfactant to the nonionic surfactant is too small or too large, the stain stain cleaning performance intended by the present invention may not be obtained.

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, a benzyl group, and 2 to 4 carbon atoms, preferably 2 to 2 carbon atoms. 3 represents a hydroxyalkyl group or a polyoxyalkylene group.)
Examples of amphoteric surfactants include amphoteric surfactants such as imidazolines and amide betaines.
Examples of the semipolar surfactant include amine oxide.
When a cationic surfactant and an amphoteric surfactant are included, the blending amount is preferably 0.1 to 3% by mass, and more preferably 0.1 to 1%.

Although the compounding quantity of the said (C) component in the bleach composition of this invention is not restrict | limited in particular, It is good that it is 1-20 mass%, Preferably it is 5-18 mass%. When the blending amount of the total amount of the component (C) is too small, it may be difficult to obtain a sufficient cleaning effect, and if it is too much, the cleaning performance may not be improved and may be saturated.
Although the compounding quantity of the said (C) component in the bleaching detergent composition of this invention is not restrict | limited in particular, It is good that it is 10-30 mass%, Preferably it is 15-25 mass%. When the blending amount of the total amount of the component (C) is too small, it may be difficult to obtain a sufficient cleaning effect, and if it is too much, the cleaning performance may not be improved and may be saturated.
In the present invention, the surfactant can be blended in the composition of the present invention as it is, or can be blended as particles containing a cleaning builder, a dissolution accelerator, etc. described later. From the viewpoint of improving the solubility, it is preferable to blend as particles containing a cleaning builder.

(D) component of this invention is an amylase whose viscosity reduction rate computed by Formula (1) mentioned above is 40% or more.
Specifically, 25 g of corn starch (manufactured by Kanto Chemical Co., Inc.) was added to 475 g of an aqueous alkali (sodium carbonate 4000 ppm) solution at 90 ± 2 ° C., stirred and dissolved at 90 ± 2 ° C. for 1 hour, and then 12 hours at 5 ° C. Cooling. Then, it is allowed to stand at room temperature, and after the temperature of the solution becomes equal to room temperature, the temperature is adjusted to 25 ° C. Next, the viscosity (mPa · s) of 40 g of the solution adjusted to 25 ° C. was measured using a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS304-CSP-H, vibrator Shape and size: disk shape, measured at t (thickness) = 0.1 mm, φ (diameter) = 13 mm) and set as initial viscosity (measurement condition: set amplitude value 50 mV, vibration frequency: 30 Hz, sample amount) : 40 g (as 5% aqueous solution), measurement temperature: 25 ° C.). Thereafter, 0.004 mg of amylase as the amount of enzyme protein was quickly added to 40 g of the starch aqueous solution whose initial viscosity was measured and stirred, and the viscosity was measured in the same manner as the initial viscosity 10 seconds after the addition, and then the temperature was adjusted at 25 ° C. . Then, after 10 minutes, 30 minutes and 60 minutes, the viscosity is measured in the same manner as the initial viscosity.
The viscosity reduction rate (%) can be calculated by substituting the obtained initial viscosity and the value of the viscosity after 60 minutes into the above formula (1).
Amylase satisfying the specific viscosity reduction rate can be appropriately selected by a simple screening method using the above-described commercially available apparatus (CJV5000 manufactured by A & D Co., Ltd.).

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 types are used in combination, even if the viscosity reduction rate for each amylase is less than 40%, if the viscosity reduction rate when used in combination is 40% or more, it is used as the component (D) of the present invention. can do. As the component (D) of the present invention, in order to effectively remove the composite dirt, the starch contained in the composite dirt is more effectively decomposed, and it is easy to remove with a preferable t that reduces the viscosity of the dirt. An amylase having an excellent effect is preferable. Specifically, an amylase having a viscosity reduction rate of 50% or more is preferable, an amylase having a viscosity reduction rate of 70% or more is more preferable, and an amylase having a viscosity reduction rate of 80% or more is more preferable. Although not bound by any theory, if the viscosity reduction rate of amylase is 40% or more, the adhesion between clothes and dirt can be weakened, so it exhibits a high removal effect against spilled dirt. It is considered a thing. By selecting an amylase having a high viscosity reducing effect or by selecting an amylase mutated to increase the viscosity reducing effect, the viscosity reduction rate of the amylase can be increased. In particular, the amylases described in the above patent publications (21) to (33) are preferable. In particular, a stainzyme is preferable.

  Amylase is preferably used as a granulated product with a stabilizer, a filler, a filler, a whitening agent, a binder, a coating agent and the like based on a normal granulation method. It is because it is excellent in stability and solubility in water. From the viewpoint of stability and solubility in water, it is desirable that the average particle size measured by the method described in Examples below be 200 to 700 μm. In addition, when granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed to form the same granulated product. Usually, the amount of amylase in the enzyme granulated product is about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass as the amount of enzyme protein. . As methods for granulating enzyme-containing particles, JP-A No. 53-6484, JP-A No. 60-262900, JP-A No. 62-257990, JP-A No. 1-112983, JP-A No. 3-129, No. 503775, JP-A-4-503369, JP-A-2000-178593, and the like.

In the composition of the present invention, (D) amylase is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and particularly preferably 0.003 as the amount of enzyme protein based on the total amount of the composition. It is preferably contained in an amount of not less than 0.05% by weight, preferably not more than 0.05% by weight, more preferably not more than 0.03% by weight, particularly preferably not more than 0.02% by weight. When the amount is less than 0.001% by mass, the effect of the present invention may be reduced. When the amount is more than 0.05% by mass, the effect may reach a peak.
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.

In addition to the above essential components, the bleaching detergent composition of the present invention can contain the following various components that are usually blended in a detergent composition within a range that does not interfere with the effects of the present invention.
(1) Builders Examples of builders include inorganic builders and organic builders.
Examples of inorganic builders include, for example, alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate, sodium sulfate, potassium sulfate, Neutral salts such as sodium chloride and potassium chloride, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc.
_{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.

Moreover, when mix | blending what shows low-temperature solubility improvement effects, such as potassium carbonate, sodium chloride, potassium chloride, among the said inorganic builder, 2-15 mass% in the bleaching detergent composition of this invention, From Preferably, 4 to 10% by mass is blended.
In addition, inorganic builder can also be mix | blended in the composition of this invention by forming particle | grains with surfactant as stated above, and can also mix | blend separately from surfactant containing particle | grains. . When blending (powder mixing) separately from the surfactant-containing particles, from the viewpoint of solubility at a low water temperature, an inorganic or builder is used as the core particle, and the core particle is an organic or inorganic water solution that is the first surface treatment agent. It is preferable that the surface-treated inorganic builder particles are surface-treated with a conductive polymer compound and the treated surface is treated with a poorly water-soluble compound as a second surface treating agent. In this case, the inorganic builder is preferably a water-soluble alkaline inorganic compound, and more preferably a carbonate. As the first surface treating agent, a carboxylic acid polymer is preferable, an acrylic acid polymer is more preferable, and a sodium salt of a copolymer of acrylic acid and maleic acid is most preferable. As the second surface treatment agent, a higher fatty acid having 12 to 16 carbon atoms is preferable, and lauric acid is more preferable.

As an optimal example of the surface-treated inorganic builder particles, the surface of sodium carbonate particles was treated with a sodium salt of a copolymer of acrylic acid and maleic acid as a first surface treating agent and lauric acid as a second surface treating agent. And surface-treated sodium carbonate particles.
The water-soluble polymer compound as the first surface treatment agent is preferably used in an amount of 0.1 to 10% by mass, particularly 0.5 to 8% by mass, based on the core particles. If the amount is less than 0.1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the core particles may be too small.

The poorly water-soluble compound as the second surface treatment agent is preferably used in an amount of 0.1 to 10% by mass, particularly 2 to 8% by mass, based on the core particles surface-treated with the first surface treatment agent. If the amount is less than 0.1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the core particles may be too small.
The surface-treated sodium carbonate particles are blended in the bleaching detergent composition of the present invention in an amount of 1 to 50% by mass, more preferably 5 to 30% by mass, and most preferably 10 to 20% by mass.

  Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyimino Hydroxyaminocarboxylates such as disuccinate, hydroxyethylethylenediaminetriacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, Cyclocarboxylates such as benzopolycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate 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, or salts thereof; polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, or the like 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 10 to 70% by mass, particularly preferably 20 to 50% by mass in the detergent composition in order to impart sufficient detergency.
(2) As a brightening agent, bis (triazinylaminostilbene) disulfonic acid derivative (Tinopearl AMS-GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X] and the like.
(3) As a surface modifier, fine powdered calcium carbonate, fine powdered zeolite, granular zeolite, polyethylene glycol and the like.
(4) Cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone and derivatives thereof as anti-staining agents.
(5) As a porous oil absorbent, amorphous anhydrous silicic acid, calcium silicate, etc.
(6) As a flexibility imparting agent, cationic surfactants such as dialkyl quaternary ammonium salts, clay minerals such as smectite, and the like.
(7) Silicone oil or the like as an antifoaming agent.
(8) Perfume (9) Coloring agents such as water-soluble dyes and pigments

(10) Enzymes other than component (D) Commercially available enzyme particles that are currently used in granular laundry detergents can be used as they are for enzymes other than the specific amylase (D).
Examples of the amylase other than the component (D) include the enzymes described in JP-A-2001-64695 [0011]. Examples of commercially available enzymes include Novozymes Termamyl, Duramil, and Genencor. And maxamyl.
Enzymes other than amylase (which are enzymes that inherently perform enzyme action during the washing process) are classified according to 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).
Specific examples of cellulase include cellzyme, carezyme (manufactured by Novozymes), KAC500 (manufactured by Kao Corporation), and cellulase described in claim 4 of JP-A No. 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.
Preferable formulation examples of the composition of the present invention include the following:
(A) Sodium percarbonate coated with or not coated with a coating agent: 3 to 50% by mass,
(B) A bleach activator selected from the group consisting of 4-decanoyloxybenzoic acid, sodium 4-dodecanoyloxybenzenesulfonate and sodium 4-decanoyloxybenzenesulfonate is contained in an amount of 50 to 80% by mass. The granulated product is 0.1 to 10% by mass as the amount of granulated product,
(C) LAS having an alkyl group having 10 to 14 carbon atoms, higher fatty acid having 10 to 20 carbon atoms, α-SF having 12 to 28 carbon atoms, and aliphatic alcohol having 12 to 16 carbon atoms and 2 to 4 carbon atoms 20 to 40% by mass of at least one surfactant selected from the group consisting of polyoxyalkylene alkyl ethers with an average addition of 5 to 20 mol of ethylene oxide, and (D) calculated by the above formula (1) Amylase having a viscosity reduction rate of 90% or more: 0.001 to 0.05% by mass (as enzyme protein amount),
A bleaching composition comprising:
Furthermore, it is particularly preferable to contain 0.001 to 0.02% by mass (as the amount of enzyme protein) of protease and 0.001 to 0.01% by mass (as the amount of enzyme protein) of lipase.

The bleaching detergent composition of the present invention may be granular or solid, and its preparation method is not particularly limited. For example, if used as a high bulk density detergent, the above (A) to (D) It can be prepared by preparing high bulk density detergent particles containing components according to a conventional method and mixing the detergent particles with a granulated product of a bleaching inorganic peroxide and a bleach activator.
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 detergent 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 from the viewpoint of solubility and stability. ~ 600 μm.
The bleaching composition of this invention is used suitably as a washing | cleaning agent for clothes or a bleaching agent, The usage method in particular is not restrict | limited, It can be used by a conventional method.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, “%” indicates mass%, and the ratio indicates mass ratio.
1. (A) Measurement of viscosity reduction rate of amylase 25 g of corn starch (manufactured by Kanto Chemical Co., Inc.) was added to 475 g of an aqueous alkali (sodium carbonate 4000 ppm) solution at 90 ± 2 ° C., and stirred and dissolved at 90 ± 2 ° C. for 1 hour. Cooled at 5 ° C. for 12 hours. Thereafter, the solution was allowed to stand at room temperature, and after the temperature of the solution became equal to room temperature, the temperature was adjusted to 25 ° C. Next, the viscosity of 40 g of the solution adjusted to 25 ° C. was measured using a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS304-CSP-H, vibrator shape and size: Disk shape, t (thickness) = 0.1 mm, φ (diameter) = 13 mm) were used as initial viscosity (measurement condition: set amplitude value 50 mV, vibration frequency: 30 Hz, sample amount: 40 g (5% As an aqueous solution), measuring temperature: 25 ° C.). Thereafter, 0.004 mg of amylase as an enzyme protein amount was rapidly added to 40 g of an aqueous starch solution and stirred, and 10 seconds after the addition, the viscosity was measured in the same manner as the initial viscosity, and then the temperature was adjusted at 25 ° C. Then, after 10 minutes, 30 minutes and 60 minutes, the viscosity was measured in the same manner as the initial viscosity. The initial viscosity and the viscosity value after 60 minutes were obtained. Next, the viscosity reduction rate was calculated according to the above-described formula (1).
When the viscosity reduction ratios of Stainzyme (manufactured by Novozymes), Termamyl (manufactured by Novozymes) and Duramil (manufactured by Novozymes) were measured by the above method, they were 91%, 20% and 23%, respectively. These values are average values of three experiments. Moreover, the fluctuation range of the measured value was about 10 mPa · s. The relationship between time and viscosity for each enzyme is shown in FIG.

2. Method for preparing bleach detergent composition
(i) Method for preparing bleach detergent composition (Part 1)
Among the detergent compositions shown in Table 1, Examples 1 to 5 and 8 and Comparative Examples 9 to 10 and 12 were prepared by the following procedure.
First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, surfactants (LAS-K, LAS-Na, AOS-K, soap) excluding α-SF-Na and nonionic surfactant were added and stirred for 10 minutes. Subsequently, an acrylic acid polymer and an optical brightener were added. After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount for kneading addition described later, 3.2% equivalent amount for grinding aid, 1.5% equivalent amount surface) Sodium carbonate and potassium carbonate were added except for zeolite A for coating). The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray-dried particles with mL and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.
The above-mentioned spray-dried particles, this mixed concentrate, 2.0% equivalent amount of A-type zeolite, nonionic surfactant and water were put into a continuous kneader (Kurimoto Steel Works, KRC-S4 type), Kneading was performed under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded material. This surfactant-containing kneaded product was cut with a cutter while extruding it with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed was 5 m / m). s) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) Crush using a Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in three stages below (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, Rotational speed: 1st stage / 2nd stage / 3rd stage 4,700 rpm), surfactant-containing particles (average particle diameter 500 μm, bulk density 0.85 g / mL) were obtained.
Furthermore, filled with a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum internal wall surface of the container 131.7L and two baffle plates with a clearance of 20 mm from the internal wall surface and a height of 45 mm) (A) component percarbonate, component (B) bleach activator granulated product, surfactant-containing particles described above, (D) Particles containing amylase as a component, particles containing other enzymes, surface-treated sodium carbonate particles, layered silicate, fine powder type A zeolite for surface coating equivalent to 1.5% of the total amount of bleaching detergent composition Then, while spraying 0.5% equivalent amount of nonionic surfactant and fragrance, the mixture was rolled for 1 minute to modify the surface to obtain a mixed particle group. In order to color a part of the obtained mixed particle group, the particle group was transferred on a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor had a height of 30 mm and a layer width). 300 mm) A 20% aqueous dispersion of the dye was sprayed on the surface to obtain a high bulk density granular bleaching detergent composition having the composition shown in Table 1. The bulk density and average particle diameter of the resulting high bulk density granular bleaching detergent composition were as described in Table 1. About the high bulk density bleach detergent composition, the washing | cleaning performance with respect to a food spilling stain | pollution | contamination was evaluated in accordance with 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, Examples 6 to 7 and Comparative Example 11 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 a fluorescent brightening agent were added thereto, and after stirring for 10 minutes, sodium carbonate was added, and then an acrylic acid polymer was added. After further stirring for 10 minutes, sodium chloride and a part of powdered zeolite were 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 (bulk density 0.75 g / mL, average particle size 300 μm).
A part (2% by mass) of the above powdered zeolite is mixed with this detergent composition with a V blender, and then the enzyme, percarbonate, surface-treated sodium carbonate particles and bleach activator granulated product are mixed with the 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 bulk density and average particle diameter of the resulting high bulk density granular bleaching detergent composition are as shown in Table 1. About the high bulk density granular bleaching detergent composition, the washing | cleaning performance with respect to a food spilling stain | pollution | contamination was evaluated according to the following evaluation method. The results are also shown in Table 1.

3. Preparation Method of Bleach Composition A bleach composition shown in Table 2 was prepared by the following procedure. Each component except percarbonate, bleach activator granulated product, enzyme, fragrance, pigment, surfactant, and surface-treated sodium carbonate particles was put into 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.
A percarbonate, a bleach activator granulated product, surface-treated sodium carbonate particles, and an enzyme were mixed with the mixed granule using a V blender to obtain a bleach composition. Table 2 shows the bulk density and average particle size of the resulting bleaching composition. About the bleaching composition, the washing | cleaning performance with respect to a food spilling stain | pollution | contamination was evaluated according to the following evaluation method. The results are also shown in Table 2.

4). Preparation method of bleach activator granulation product (i) Preparation method of bleach activator granulation product A 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleach activator, 70 parts by mass, PEG [ Polyethylene glycol # 6000M (manufactured by Lion Co., Ltd.)] 20 parts by mass, sodium α-olefin sulfonate powder product having 14 carbon atoms (Lipolane PJ-400 (manufactured by Lion Co., Ltd.)) to a total of 5000 g Thus, it was put into an Extrude Ohmic EM-6 type manufactured by Hosokawa Micron Co., Ltd. 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-dodecanoyloxybenzenesulfonate was used as the bleach activator. B was prepared.
(Iii) Method for preparing bleach activator granulated product C Bleach activator granulated product in the same manner as bleach activator A except that sodium 4-decanoyloxybenzenesulfonate was used as the bleach activator. C was prepared.

5. Method for producing surface-treated sodium carbonate particles (cleaning builder) Proshear mixer (Ohira) with 85.5 parts by weight of sodium carbonate (granular ash manufactured by Asahi Glass Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm The mixture was put into Yoki Co., Ltd. (filling rate: 30% by volume), and stirring was started at a spindle of 150 rpm (chopper rotation speed: 1015 rpm, blade tip speed (circumferential speed): 6.9 m / s). Later, 7.5 parts by weight of sodium salt of acrylic acid / maleic acid copolymer (Nippon Shokubai Aqualic TL-400, 40% solid content aqueous solution) is sprayed for 180 seconds with a pressure nozzle (flat nozzle) with a spray angle of 115 degrees. After adding, granulation and coating operations were performed.
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 plow shear mixer. Stirring was continued for 30 seconds to obtain particles.
Next, the obtained particles are filled 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 surface-treated sodium carbonate 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). Meat sauce dirt cleaning performance evaluation (i) Preparation method of meat sauce dirt evaluation cloth No. 60 cotton plain weave cloth was cut into 20 cm x 30 cm, and a can of kagome ripe tomato was soaked in a stainless steel vat for about 1 hour. Thereafter, solids adhered to the surface were removed, and air-dried overnight in a dark and constant temperature and humidity chamber at 20 ° C. and 40% RH was used as a meat sauce stain evaluation cloth.
(Ii) Evaluation of cleaning performance of high bulk density granular bleaching detergent composition Using Teg-O-meter of Testing USA as a cleaning tester, put the above 5 stain stain evaluation cloth, sebum cloth, washing knitted cloth, The high bulk density granular bleaching detergent composition shown in Table 1 and Table 2 was added so that the detergent concentration would be 0.067%, and washed at 120 rpm and 20 ° C. for 10 minutes according to the bath ratio of 30 times. The water used was 4 ° DH, the amount of the cleaning solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the stain stain evaluation cloth was dried, and the washing rate was calculated by the following equation.
Detergency (%) = (K / S of contaminated cloth−K / S of washed cloth) × 100 /
(K / S of contaminated cloth-K / S of uncontaminated cloth)
Here, K / S = (1−R / 100) 2 / (2R / 100) (where R is reflectance (%)). The reflectance was measured using a 460 nm filter with Σ90 (manufactured by Nippon Denshoku Industries Co., Ltd.).

(Iii) Stain stain cleaning performance evaluation of bleaching composition Using Teg-O-meter of Testing USA as a cleaning tester, put the above-mentioned 5 stain stain evaluation fabrics, sebum fabric and cleaning knitted fabric into Table 3. The bleach composition shown is added so that the detergent concentration is 0.033%, and at the same time, a commercial detergent (Lion Corporation Top, Lot No. 010222C4B) is added so that the detergent concentration is 0.05%. Washing was performed at 120 rpm and 20 ° C. for 10 minutes in accordance with the bath ratio of 30 times. The water used was 4 ° DH, the amount of the cleaning solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the stain stain evaluation cloth was dried, and (ii) the cleaning rate was calculated by the method for evaluating the cleaning performance of the high bulk density granular bleaching detergent composition.

7). Measurement of average particle diameter For each sample and a mixture thereof, using a 9-stage sieve and a saucer having openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm Classification operation was performed. In the classification operation, a sieve with a small opening and a sieve with a large opening are stacked in the order of the sieve, and a base sample of 100 g / time is put on the top of the top sieve of 1,680 μm, and the lid is covered and a low-tap type sieve shaker Attached to (made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and vibrated for 10 minutes, the samples remaining on each sieve and the saucer were collected for each sieve mesh. The mass of the sample was measured. When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle size (weight: 50%) was calculated by the following equation, where c% was the cumulative mass frequency from the sieve to the aμm sieve and d% was the mass frequency on the aμm sieve.

8). Measurement of bulk density The bulk density was measured according to JIS K3362-1998.
The components used in the above examples are as follows.
(A) Component percarbonate A: coated sodium percarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd. SPC-D, average particle size of about 750 μm)
Percarbonate B: Sodium percarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd. SPC-Z, average particle size of about 500 μm)
(B) Component bleach activator granulated product A: Bleach activator granulated product obtained by the method for preparing the bleach activator granulated product A Bleach activator granulated product B: Bleach activator Bleach activator granulated product obtained by the preparation method of granulated product B Bleach activator granulated product C: Bleach activator granulated product obtained by the above-described method of preparing bleach activator granulated product C

(C) component α-SF-Na: sodium salt of α-sulfo fatty acid methyl ester having 14 carbon atoms: 16 carbon atoms = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder being 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: Diadol 13 (Mitsubishi Chemical Co., Ltd.) ethylene oxide average 8 mol adduct (90% pure)

(D) Component amylase A: Stainzyme 12T (manufactured by Novozymes)
Amylase B: Termamyl 120T (manufactured by Novozymes)
[Builders, etc.]
Surface-treated sodium carbonate particles: Surface-treated sodium carbonate particles obtained by the above-described method for producing surface-treated sodium carbonate particles Lauric acid: NAA-12, manufactured by NOF
Sodium carbonate: Heavy sodium carbonate (Soda ash manufactured by Asahi Glass Co., Ltd., trade name: granular 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.)
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 (Nippon Shokubai Aquaric TL-400)
Acrylic acid polymer B: Sodium polyacrylate, trade name Socaran PA30 (BASF)
Optical brightener: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) and Chinopearl AMS-GX (manufactured by Ciba Specialty Chemicals) with a mass ratio of 8/2

[Any enzyme]
Protease A: Sabinase 12T (Novozymes)
Protease B: Everase 8T (Novozymes)
Lipase: Lipex 50T (manufactured by Novozymes)
Cellulase: Cellzyme 0.7T (manufactured by Novozymes)
[Dye]
Dye A: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue)
Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo)
Dye C: A spherical resin particle having an average particle size of 0.35 μm obtained by radical emulsion polymerization in an aqueous dispersion using acrylonitrile / styrene / acrylic acid as a constituent monomer, and about 1% C.I. I. An aqueous dispersion of a pink fluorescent pigment obtained by adding BASIC RED-1 to a polymerization resin suspension and subjecting it to a heat treatment.
[Fragrance]
Fragrance A: Fragrance composition A shown in Tables 11 to 18 of JP-A-2002-146399
Fragrance B: Fragrance composition B shown in Tables 11 to 18 of JP-A-2002-146399
Fragrance C: Fragrance composition C shown in Tables 11 to 18 of JP-A-2002-146399
Fragrance D: Fragrance composition D shown in Tables 11 to 18 of JP-A-2002-146399

FIG. 1 is a graph showing changes in viscosity over time for three types of amylases (Termamyl, Duramil and Steinzyme).

Claims (3)

Bleaching composition characterized by containing the following components:
(A) a peroxide that releases hydrogen peroxide in water;
(B) a bleach activator represented by the following formula (I) or (II):
_{RCOO-C 6 H 4 -COOM (} I)
_{RCOO-C 6 H 4 -SO 3} M (II)
(In formulas (I) and (II), R represents a linear or branched alkyl group or alkenyl group having 9 to 11 carbon atoms, and M represents hydrogen or a salt-forming cation.)
(C) Surfactant and (D) Amylase whose viscosity reduction rate calculated by the following formula (1) is 40% or more.

  The bleaching composition according to claim 1, wherein the amylase as component (D) has a viscosity reduction rate of 50% or more.   The bleaching composition according to claim 2, wherein the amylase as component (D) is Steinzyme (registered trademark).

Images