JP2006131659A - Bleaching composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching composition having a high suppressing effect against the smell and yellowing of clothes. <P>SOLUTION: This bleaching composition comprises (A) a peroxide forming hydrogen peroxide by being dissolved with hydrogen peroxide water or water, (B) a metal catalyst, and (C) a lipase having an enzymatic activity of showing ≥2 folds (molar ratio) amount of a fatty acid production from triolein after a substrate decomposition test to the fatty acid production amount from palmitic acid-n-hexadecyl after the substrate decomposition test. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a granular or solid bleaching composition, and more particularly to a bleaching composition having a high inhibitory effect on odor and yellowing of clothing.

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 a bleaching agent, an oxygen-based bleaching agent is widely used because it does not lose color even when applied to a colored fabric of clothing, and sodium percarbonate is a typical bleaching substrate.
In addition, a bleach activator is used in combination as a base for enhancing the bleaching effect. 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.
On the other hand, much research has been conducted on metal catalysts composed of transition metals and ligands. In the method using a metal catalyst, a mechanism is proposed in which a complex catalytically activates hydrogen peroxide in a bleaching solution and reacts with a dye to bring a high bleaching effect to stain stains (for example, non-patent literature). 1, 2). Therefore, high bleaching power can be efficiently obtained with a small amount of complex.
However, in order to remove lipid stains, a sufficient effect may not be obtained with a bleaching substrate alone, and enzymes such as lipases are also used (for example, Patent Documents 1 to 4). However, although lipase has an effect on soils having lipids containing ester bonds (such as triglycerides), it cannot be expected to have a high effect on suppressing the generation of odor and yellowing due to their degradation products (such as fatty acids). An excellent bleaching composition that suppresses the occurrence of yellowing has been desired.

JP 2004-204084 A Japanese translation of PCT publication No. 2003-508587 JP 2002-537484 A Japanese Patent Laid-Open No. 11-515049 Nature, VOL. 369 (1994) 637-639 J. et al. Am. Chem. Soc. , VOL. 115 (1993) 1772-1773.

  An object of this invention is to provide the bleaching composition which has a high inhibitory effect with respect to the smell and yellowing of clothing in view of the said situation.

As a result of intensive studies to solve the above problems, the present inventors can achieve the above object by using inorganic peroxides and metal catalysts that release hydrogen peroxide in water and specific lipases. As a result, the present invention has been completed.
That is, the present invention comprises (A) hydrogen peroxide or a peroxide that dissolves in water to generate hydrogen peroxide, (B) a metal catalyst, (C) a fatty acid from n-hexadecyl palmitate after a substrate decomposition test Provided is a bleaching composition containing a lipase having an enzyme activity in which the amount of fatty acid produced from triolein after a substrate decomposition test is 2.0 times or more (molar ratio) relative to the amount produced.

  ADVANTAGE OF THE INVENTION According to this invention, the bleaching composition excellent in suppression of generation | occurrence | production of a smell and yellowing can be provided.

  The bleaching composition of the present invention comprises (A) hydrogen peroxide or a peroxide that generates hydrogen peroxide when dissolved in water, (B) a metal catalyst, (C) n-hexadecyl palmitate after a substrate decomposition test The lipase which has the enzyme activity from which the fatty-acid production amount from the triolein after a substrate decomposition test becomes 2.0 times or more (molar ratio) with respect to the fatty-acid production amount from is contained.

  The bleaching composition of the present invention is a generic name for powder detergents, granular detergents with high bulk density (high bulk density detergents), solid detergents such as tablet type or briquette type, sheet detergents, and powder bleaches. Especially, it is more suitable when it prepares as a high bulk density detergent and a powder bleach. The high bulk density detergent usually means a granular detergent having a bulk density of 0.6 g / mL or more.

  The component (A) of the present invention is hydrogen peroxide or an inorganic peroxide that releases hydrogen peroxide in water. Specific examples of the component (A) include sodium percarbonate, sodium perborate, sodium perborate trihydrate and the like. From the viewpoint of solubility during use and stability during storage, percarbonate is used. Sodium is preferably used. Further, when used in a detergent containing zeolite, it is preferable to use sodium percarbonate coated with an inorganic or organic compound for stabilization. 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.

  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 is a particle diameter with a cumulative mass of 50% calculated from the particle size distribution obtained using a sieve. Although the compounding quantity of (A) 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 to 20 mass% is preferable in a composition, More preferably, it is 2 to 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 less than the said range, a bleaching effect may not be enough as a bleaching detergent composition.

As the metal catalyst used as the component (B) of the present invention, it acts catalytically in the bleaching solution, and continues to exhibit the bleaching effect as long as the peroxide is present. Care must be taken when using it as it may have adverse effects. (B) The metal catalyst has 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), 13,14-dichloro-6,6-diethyl-3 , 4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11-benzotetraazacyclotridecine, 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 can be mentioned. Specific metal 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, 5,12-dimethyl-1,5,8,12-tetraazabicyclo [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-benzotetra Azacyclotridecine] -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 complex, (bis (salicylideniminoethyl) methylamine) -manganese complex, etc., preferably (tris (salicylideneiminoethyl) amine) -manganese in terms of bleaching power and clothing damage and fading Complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex.
In the present invention, the preferred molar ratio of the transition metal atom to the ligand of the metal catalyst (B) in the present invention is 1: 1 to 1: 4, and if the proportion of the ligand is less 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 (B) in the bleaching composition and the bleaching detergent composition is 0.001 to 1% by mass, and in the bleaching composition, 0.01 to 0.5% by mass. More preferably, in a bleaching detergent composition, 0.005-0.3 mass% is more preferable. 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 (B) is granulated and molded using the following bleach activator granulation method 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 (B) is used as a granulated product or a molded product, the preferable content of the granulated product in the bleaching composition and the bleaching detergent composition is 0.001 to 1% by mass. In the bleaching composition, 0.1 to 1% by mass is more preferable, and in the bleaching detergent composition, 0.01 to 0.5% by mass is more preferable.

In the present invention, “lipase” refers to an enzyme classified under Enzyme Classification No. EC3.1.1 (carboxylate ester hydrolase) according to the recommendation of International Union of Biochemistry and Molecular Biology (IUBMB) (1992). That is, lipase is an enzyme that exhibits hydrolytic activity for at least one of the types of ester bonds present in at least one of the following lipids.
Lipids: mono-, di- and triglycerides, phospholipids (all types), thioesters, cholesterol esters, wax-esters, cutins, suberins, synthetic esters, etc. (see various types of ester linkages mentioned in EC 3.1.1) )
In other words, lipases include those conventionally referred to as lipases, phospholipases, esterases or cutinases, etc., and naturally occurring enzymes and one or more amino acid residues are denatured compared to naturally occurring enzymes. Including the mutants.

  Among these, the “lipase” used as the component (C) of the present invention is the amount of fatty acid produced from triolein after the substrate degradation test is 2 with respect to the amount of fatty acid produced from n-hexadecyl palmitate after the substrate degradation test. Examples of the lipase having an enzyme activity of 0 times or more (molar ratio) include lipase derived from Humicola lanuginosa described in JP-T-11-510699. Such a lipase is commercially available from Novozymes as “Lipex”. The lipase activity was measured by the following method.

The fatty acid production amount from triolein after the substrate degradation test is 2.0 times or more (molar ratio relative to the fatty acid production amount from n-hexadecyl palmitate after the substrate degradation test, which is blended in the bleaching composition of the present invention. The enzymatic activity of the “lipase having an enzymatic activity” is measured by the following substrate degradation test method.
A magnetic stirrer bar (diameter 8 mm, length 30 mm, cylindrical) is placed in a 200 mL (inner diameter 63 mm, height 80 mm) beaker, and a base solution 100 ± 0.2 mL at 22.5 ° C. ± 0.5 ° C. (α-SF -Na [sodium salt of α-sulfo fatty acid methyl ester having an alkyl group of C14 / 16 = 2/8 (mass ratio)] 200 ppm, sodium carbonate 200 ppm, German hardness 3 ° DH (calcium chloride is added to ion-exchanged water. And 0.2 g of triolein (Fulka reagent) or n-hexadecyl palmitate (Tokyo Kasei Reagent) as a substrate was added and stirred for 15 to 20 minutes to obtain a constant pH. 10 to 10.5). The apparatus used is a titrator TS-980 (manufactured by Hiranuma Sangyo Co., Ltd.) and the rotation speed is set to 200 rpm. In addition, since the pH electrode is also incorporated in the titration apparatus, this electrode is used. Next, with stirring at room temperature, an N / 10 KOH solution is added dropwise so as to maintain the initial pH value (about 10 to 10.5). One minute after the start of titration, various lipases are added so that the protein concentration of the lipase in the base solution is in the range of 0.1 to 0.01 ppm, and the amount of the N / 10 KOH solution dropped 61 minutes later is measured. The protein concentration of lipase is the same for triolein and n-hexadecyl palmitate for each lipase. The amount of KOH added for 60 minutes after adding the lipase thus determined is defined as the amount of fatty acid produced from each substrate (triolein or n-hexadecyl palmitate). The fatty acid production amount (molar ratio) of triolein relative to the fatty acid production amount from n-hexadecyl palmitate, that is, the enzyme activity, is calculated from the average value of the fatty acid production amount repeated 10 times.
In the bleaching composition of the present invention, a lipase having an enzyme activity thus determined of 2.0 times or more, preferably 2.0 to 10.0 times, more preferably 2.2 to 8.0 times. Blend.
The triolein used as a substrate in the substrate degradation test is triglyceride of oleic acid.
The reason for selecting triolein and n-hexadecyl palmitate as the substrate is as follows. That is, an ester compound that is present as a sebum component derived from the human body and that can be decomposed by lipase was selected. Triolein was selected as a liquid sebum, and n-hexadecyl palmitate was selected as a representative of solid sebum.

In addition to the above essential components, the bleaching composition of the present invention can be blended with the following various components that are usually blended into a detergent composition within a range that does not interfere with the effects of the present invention.
1) Examples of the builder 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 (M2O) .Al2O2.y1 (SiO2) .w1 (H2O) (formula In the formula, M is 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 0.8 to A crystalline aluminosilicate represented by the number of 6 and w1 represents an arbitrary positive number), general formula: x2 (M2O) .Al2O3.y2 (SiO2) .w2 (H2 (Wherein M is an alkali metal atom such as sodium or potassium, x2, y2 and w2 represent the number of moles of each component, generally x2 is a number from 0.7 to 1.2, and y2 is 1. Amorphous aluminosilicate represented by the number of .6 to 2.8, w2 is 0 or any positive number), x3 (N2O) .Al2O3.y3 (SiO2) .z3 (P2O5) .w3 (H2O) (wherein M is an alkali metal atom such as sodium or potassium, x3, y3, Z3 and w3 represent the number of moles of each component, and in general, x3 is a number from 0.2 to 1.1. , 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). Among the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, and sodium aluminosilicate are preferable.
Examples of the organic builder include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate, and other aminocarboxylates; 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) Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, and these can be used alone or in combination of two or more. .
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 3 to 30, preferably 5 to 20. R ¹⁰ may have a substituent having 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) Alkyl amine oxide Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or lower and an HLB of 9 to 16, polyoxyethylene polyoxypropylene alkyl ( Alternatively, alkenyl) ether, fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester, and the like are preferably used. 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 10 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) Bleach activator In this invention, in order to improve bactericidal power, a bleach activator can also be used together. The bleach activator is an organic peracid precursor and 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 at a high concentration, unlike the (B) metal catalyst that acts catalytically. Preferred bleach activators include sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octadecyl Noyloxybenzoic acid, Nonanoyloxybenzoic acid, Decanoyloxybenzoic acid, Undecanoyloxybenzoic acid, Dodecanoyloxybenzoic acid, Octanoyloxybenzene, Nonanoyloxybenzene, Decanoyloxybenzene, Undecanoyloxybenzene, Dodecane Examples include noyloxybenzene.
The 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.
The content of the bleach activator is preferably 0.1 to 5% by mass in the bleach composition, more preferably 0.1 to 3% by mass, and 0.05 to 3% by mass in the bleach detergent composition. Is preferable, and 0.1-1 mass% is more preferable.

4) As a brightening agent, bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt and the like.
5) As a surface modifier, finely powdered calcium carbonate, finely powdered zeolite, granular zeolite, polyethylene glycol and the like.
6) As a recontamination inhibitor, cellulose derivatives such as carboxymethyl cellulose, polyvinylpyrrolidone and derivatives thereof.
7) As a porous oil absorbent, amorphous anhydrous silicic acid, calcium silicate and the like.
8) As a flexibility imparting agent, cationic surfactants such as dialkyl quaternary ammonium salts, clay minerals such as smectite, and the like.
9) Silicone oil or the like as an antifoaming agent.
10) Fragrance 11) Coloring agents such as water-soluble dyes and pigments

12) Enzymes other than the component (C) Enzymes (enzymes that inherently perform enzyme action during the washing step) are classified according to the reactivity of the enzymes, hydrolases, oxidoreductases, lyases, transferases. And isomerases and the like, and any of them 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 amylase include Termamyl, Duramil, Stainzyme, Promozyme 200L (above, Novozymes), Maxamyl (Genencore), Examples include commercially available amylases such as pullulanase Amano, DB-250, and pullulanase derived from Aerobacter aerogenes ATCC 9621 (crude or crystallized product released from Seikagaku Corporation). 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.
In particular, it is preferable to combine the component (C) with protease and amylase from the viewpoint of suppressing odor.
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.

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 containing the above components (A) to (C) Can be prepared by mixing the detergent particles with a bleaching inorganic peroxide and a granulated product of a metal 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. 600 μm.
The bleaching detergent composition of the present invention is suitably used as a garment cleaning agent, 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 concretely, this invention is not restrict | limited to the following Example.
(1) Preparation method of high bulk density granular bleach detergent composition
(i) Method for preparing high bulk density granular bleaching detergent composition (Part 1)
Among the detergent compositions shown in Table 1, Examples 1 to 5 and Comparative Examples 8, 9, and 11 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, sodium percarbonate, metal catalyst granulated product, bleach activator granulated product, enzyme and layered silicate are mixed with a tumbling drum, and further, 20% aqueous pigment dispersion and fragrance are spray added. 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 composition, the performance with respect to generation | occurrence | production suppression of an odor and yellowing was evaluated in accordance with the following evaluation method. The results are also shown in Table 1.

(ii) Preparation method of high bulk density granular bleaching detergent composition (Part 2)
Among the detergent compositions shown in Table 1, Examples 6 to 7 and Comparative Example 10 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.
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 washing | cleaning and bleaching performance with respect to an odor and yellowing were evaluated in accordance with 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. The bleaching composition was evaluated for washing / bleaching performance against odor and yellowing according to the following evaluation method. The results are also shown in Table 1. The results are also shown in Table 2.

(3) Method for preparing metal catalyst granulated product Metal catalyst granulated products A, B, C, and D were obtained by the following method.
(I) Preparation method of metal catalyst granulated product A 10 parts by mass of (tris (salicylideneiminoethyl) amine) -manganese complex as a metal catalyst, cellulose powder (powder cellulose (trade name: Arbocel BE600 / 30, Rettenmeier) 10 parts by weight of nonionic surfactant (Diadol 13 (manufactured by Mitsubishi Chemical Corporation)) and 10 parts by weight of PEG # 6000 (product) Name: PEG # 6000M, manufactured by Lion Co., Ltd.) is uniformly powdered so as to have a ratio of 70 parts by mass, put into the Extrude Ohmic EM-6 model manufactured by Hosokawa Micron, kneaded and extruded. A pellet-shaped molded product having a diameter of 0.8 mmφ and a length of 0.5 to 3 mm was obtained by cutting with a cutter (kneading temperature 60 ° C., extrusion) Temperature 20 ℃ after cutting). Next, the molded product was introduced into a Fitzmill DKA-3 type manufactured by Hosokawa Micron Corporation, and pulverized and sieved to prepare a granulated product A having a size of 400 to 1000 μm.
As the metal catalyst, a complex having a ligand represented by the following formula (I) was used.

Synthesis of (tris (salicylideneiminoethyl) amine) -manganese complex Tris (2-aminoethyl) amine (reagent made by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (reagent made by Tokyo Chemical Industry Co., Ltd.), chloride Using manganese tetrahydrate (a reagent manufactured by Kanto Chemical Co., Inc.), methanol (a reagent manufactured by Kanto Chemical Co., Ltd.), ethanol (a reagent manufactured by Kansu Chemical Industry Co., Ltd.), synthesis was performed 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 1).

(ii) Preparation method of metal catalyst granulated product B
[Method of preparing metal catalyst granulated product B]
The metal catalyst granulated product B was prepared in the same manner as the metal catalyst granulated product A except that (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex was used as the metal catalyst. Prepared.
As the metal catalyst, a complex having a ligand represented by the following formula (II) was used.

[Synthesis of (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex]
Materials include ethylenediamine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dihydroxybenzaldehyde (a reagent manufactured by Kanto Chemical Co., Ltd.), manganese chloride tetrahydrate (a reagent manufactured by Kanto Chemical Co., Ltd.), methanol ( Using Kanto Chemical Co., Ltd. reagent) and ethanol (Gansu Chemical Industry Co., Ltd. reagent), the synthesis was performed by the following 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).

[Method for preparing metal catalyst granulated product C]
A metal catalyst granulated product C was prepared in the same manner as the metal catalyst granulated product A except that bis (salicylideneimino-2-ethyl) methylamine-manganese complex was used as the metal catalyst.
As the metal catalyst, a complex having a ligand represented by the following formula (III) was used.

[Synthesis of bis (salicylideneimino-2-ethyl) methylamine-manganese complex]
Materials include N'-methyl-2,2'-diaminodiethylamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), manganese chloride tetrahydrate (Kanto Chemical Co., Ltd.) Using the following method, synthesis was performed using a reagent (produced reagent), methanol (a reagent manufactured by Kanto Chemical Co., Inc.), and ethanol (a reagent manufactured by Kansu Chemical Industry Co., Ltd.).
50 ml of a methanol solution of 1.92 g (16.38 mmol) of N′-methyl-2,2′-diaminodiethylamine and 50 ml of a methanol solution of 4.00 g (32.76 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 (salicylideneimino-2-ethyl) methylamine (yield 100%).
Dissolve 1.3 g (4.0 mmol) of the bis (salicylideneimino-2-ethyl) methylamine crystal obtained above and 0.79 g (4.0 mmol) of manganese chloride tetrahydrate in 20 mL of methanol. And left at room temperature for 1 week. The precipitated crystals were separated by filtration, washed with methanol, and dried to obtain 0.33 g of bis (salicylideneimino-2-ethyl) methylamine-manganese complex (catalyst 4).

[Method for preparing metal catalyst granulated product D]
A metal catalyst granulated product D was prepared in the same manner as the metal catalyst granulated product A except that bis (salicylideneimino-2-ethyl) amine-manganese complex was used as the metal catalyst.
As the metal catalyst, a complex having a ligand represented by the following formula (IV) was used.

[Synthesis of bis (salicylideneimino-2-ethyl) amine-manganese complex]
Diethylenetriamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), manganese chloride tetrahydrate (reagent manufactured by Kanto Chemical Co., Ltd.), methanol (Kanto Chemical Co., Ltd.) The reagent was synthesized by the following method using ethanol (a reagent manufactured by Gansu Chemical Industry Co., Ltd.).
50 ml of a methanol solution of 1.68 g (16.28 mmol) of diethylenetriamine and 50 ml of a 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 (salicylidenimino-2-ethyl) amine (yield 100%).
Dissolve 1.0 g (3.2 mmol) of the crystals of bis (salicylidenimino-2-ethyl) amine obtained above and 0.63 g (3.2 mmol) of manganese chloride tetrahydrate in 20 ml of methanol. And left at room temperature for 4 days. The precipitated crystals were collected by filtration, washed with methanol, and dried to obtain 0.54 g of bis (salicylideneimino-2-ethyl) amine-manganese complex (catalyst 4).

(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 Corporation)] 20 parts by mass, sodium α-olefin sulfonate powder product having 14 carbon atoms [Lipolane PJ-400 (manufactured by Lion Corporation)] 5 parts by mass As such, it was supplied to an Extrude Ohmic EM-6 type manufactured by Hosokawa Micron Co., Ltd. and kneaded and extruded (kneading temperature 60 ° C.) to obtain a noodle-shaped extruded product having a diameter of 0.8 mmφ. This extruded product (cooled to 20 ° C by cold air) was introduced into Hosokawa Micron's Fitzmill DKA-3 type, and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent and pulverized to obtain an average particle size. A bleaching activator granulated product A having a diameter of about 700 μm was obtained.

(Ii) Preparation method of bleach activator granulation B Bleach activator was the same as bleach activator granulation A except that sodium 4-dodecanoyloxybenzenesulfonate was used as the bleach activator. A granulated product B was prepared.

Method for synthesizing sodium 4-dodecanoyloxybenzenesulfonate As raw materials, sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), lauric acid chloride ( Synthesis was performed by the following method using Tokyo Chemical Industry Co., Ltd. reagent) and acetone (Kanto Chemical Co., Ltd. reagent).
100 g (0.46 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of dimethylformamide, and lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a magnetic stirrer. After completion of the dropwise addition, the reaction was carried out for 3 hours. Dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then recrystallized in a water / acetone (= 1/1 mol) solvent. . The yield was 90%.

(4) Evaluation of inhibition performance against “smell” and “yellowing” (i) Preparation of triolein-adhering cloth Triolein (Kanto Chemical) is dissolved in chloroform (Kanto Chemical) to prepare a 4.375% solution, 100 cm 2.0 mL was dripped on No. ² skin shirt (1.75 g, BVD) and naturally dried until chloroform was completely volatilized.
(Ii) Evaluation of washing experiment of high bulk density granular bleaching detergent composition After adding to tap water (7 L, 20 ° C.) to a concentration of 0.05% by mass shown in Table 1 and stirring for 10 minutes Then, 6 sheets of (i) triolein-attached contaminated cloth prepared by the above method were put into an electric bucket (Matsushita Electric Industrial Co., Ltd.). After stirring for 1 minute, it was immersed for 14 hours, further stirred for 9 minutes, and then rinsed with tap water for 3 minutes twice.
The evaluation of odor was carried out on five evaluators after the rinsed triolein-attached contaminated cloth was dried at 70 ° C. for 8 hours and then cooled at room temperature for 30 minutes. Odor intensity
0: Odorless 1: Smell that can be perceived 2: Smell that understands what scent 3: Smell that can be easily sensed 4: Strong odor.
Furthermore, the average score of 5 persons was calculated | required and it determined in accordance with the following criteria from the average score.
1 point: average odor intensity is 3.5 or more and less than 4 points 2 point: average odor intensity is 3 or more and less than 3.5 points 3 points: average odor intensity is 2.5 or more and less than 3 points 4 points : The average of odor intensity is 1 point or more and less than 2.5 points 5 points: The average of odor intensity is 0 point or more and less than 1 point

For evaluation of yellowing, the triolein-adhered contaminated cloth after rinsing was dried at 70 ° C. for 17 hours, and then the b value, which is a yellow index, was measured and evaluated by the yellowing suppression rate obtained from the following formula.
(Yellowness suppression rate) = 100-((b value of contaminated cloth after washing and drying)-(b value of raw cloth))
/ ((B value of contaminated cloth before washing)-(b value of raw cloth)) x 100
The b value was measured with Σ2000 (Nippon Denshoku Industries Co., Ltd.) using a 460 nm filter. The determination was performed according to the following determination criteria.
1 point: Yellowing inhibition rate of less than 10% 2 points: Yellowing inhibition rate of 10% or more but less than 20% 3 points: Yellowing inhibition rate of 20% or more but less than 30% 4 points: Yellowing inhibition rate of 30% or more but less than 60% 5 Point: Yellowing suppression rate is 60% or more

(Iii) Cleaning Experiment Evaluation of Bleach Composition A cleaning composition 0.05 mass% concentration and a bleach detergent composition 0.08 mass% concentration shown in Comparative Example 7 in Table 1 are added to tap water (7 L, 20 ° C.). After adding and stirring for 10 minutes, the triolein-adhered contaminated cloth prepared by the above method was put into an electric bucket (Matsushita Electric Industrial Co., Ltd.). After stirring for 1 minute, it was immersed for 14 hours, further stirred for 9 minutes, and then rinsed with tap water for 3 minutes twice. After rinsing,
(Ii) Judgment was made by an evaluation method of odor and yellowing of the high bulk density granular bleaching detergent composition.

The components used in the above examples are as follows.
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)
α-SF-Na: Sodium salt of α-sulfo fatty acid methyl ester having an alkyl group having 14 to 16 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: An average of 5 moles of ethylene oxide adduct of Diadol 13 (Mitsubishi Chemical Corporation) (90% pure)
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.)
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.)
Metal catalyst granulated product A: Bleach activator granulated product obtained by the preparation method of the metal catalyst granulated product A Metal catalyst granulated product B: Bleach obtained by the preparation method of the metal catalyst granulated product B Activator granulated metal catalyst granulated product C: Bleached activator granulated product metal catalyst granulated product D obtained by the method for preparing metal catalyst granulated product C: Preparation of metal catalyst granulated product D Bleached activator granulated acrylic acid polymer A obtained by the method: sodium salt of acrylic acid / maleic acid copolymer, trade name Socaran CP7 (BASF)
Acrylic acid polymer B: Sodium polyacrylate, trade name Socaran PA30 (BASF)
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 No. PCT / JP2004 / 005910 Surface-treated water-soluble inorganic compound particles amylase having the composition of Example a1 in [Table 1] prepared according to Production method 1 (stir granulation 1) of the surface-treated water-soluble inorganic compound particles of Examples and Comparative Examples described: Steinzyme 12T (Novozymes)
Protease A: Sabinase 12T (Novozymes)
Protease B: Everase 8T (Novozymes)
Lipase: Lipex 50T (manufactured by Novozymes)
Cellulase: Cellzyme 0.7T (manufactured by Novozymes)
Bleach activator granulated product A: Bleach activator granulated product obtained by the method of preparing the bleach activator granulated product A Bleach activator granulated product B: Bleach activator granulated product B Bleached activator granulated pigment A obtained by the preparation method of the above: Ultramarine Blue (manufactured by Dainichi 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 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 (1)

(A) Hydrogen peroxide or a peroxide that dissolves in water to generate hydrogen peroxide,
(B) a metal catalyst,
(C) A lipase having an enzyme activity in which the amount of fatty acid produced from triolein after the substrate degradation test is 2.0 times or more (molar ratio) relative to the amount of fatty acid produced from n-hexadecyl palmitate after the substrate degradation test.
Bleaching composition characterized by containing.