JP2005206835A - Catalyst granule for bleaching activation and bleaching composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide catalyst granules for bleaching activation having high solubility, expressing a high bleaching capacity even in a short treating time and suppressing dyeing to a subjects to be washed, and to obtain a bleaching composition containing the same. <P>SOLUTION: This invention relates to the catalyst granules for bleaching activation comprising (A) 0.1-50 mass% of a catalyst for bleaching activation having a complex structure of a transition metal, (B) 0.1-50 mass% of a surfactant and (C) 10-90 mass% of a binder compound, wherein the amount of the transition metal formulated which does not form the complex in the granule contained in the catalyst for bleaching activation, is less than 1.0 mass%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a bleach-activated catalyst granule containing a metal complex bleaching catalyst having excellent solubility and a bleaching composition containing the same.

  At present, oxygen-based bleaching agents are widely accepted by consumers because of their features that can be used with peace of mind in colored patterns, and have become the mainstream bleaching agent for clothing. On the other hand, hydrogen peroxide, which is the main component of the oxygen bleach, is inferior to the chlorine bleach in terms of bleaching power, and can be said to be improved.

  There have been many reports on improving the bleaching power of oxygen bleaches to solve this problem. Research on organic peracid precursors that react with hydrogen peroxide in a cleaning solution to produce organic peracids and metal complexes Research is being conducted on bleaching catalyst technology that uses bismuth as a bleaching catalyst.

  As typical organic peracid precursors, tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS), decanoyloxybenzoic acid (DOBA) and the like are known.

  On the other hand, in recent years, the research on the method of utilizing a metal complex has been active, and Nature, VOL. 369 (1994) pp. 637-639 and J.P. Am. Chem. Soc. , VOL. 115 (1993) pp. 1772 to 1773, etc., and a mechanism has been proposed in which a complex catalytically activates hydrogen peroxide in a bleaching solution and brings a high bleaching effect to stain stains. Therefore, unlike an organic peracid precursor, high bleaching power can be efficiently obtained with a small amount of complex.

  However, these techniques can provide high bleaching power, but depending on the conditions of use, such as the bleaching composition coming into direct contact with the clothing at a high concentration, problems such as thinning of clothing cloth and perforation may occur. There may be a problem of fading the color of the wash. This damage and fading of the washing object is considered to be caused by oxygen active species generated by abnormal decomposition of hydrogen peroxide.

  The damage and fading of these objects to be washed are caused by high concentrations of bleaching agents, organic peracid precursors, bleach activation catalysts when the bleaching composition is not sufficiently dissolved and remains undissolved on the object to be washed. It becomes prominent when touching clothes.

  Regarding the suppression of clothing damage and fading of organic peracid precursors and bleach-activated catalysts, suppression technology by closely mixing organic peracid precursors and mineral substances such as acidic clay and bentonite (Patent Document 1: Japanese Patent Laid-Open No. Hei 11 (1994)) 6-057297), suppression technology by a combination of a catalyst and a radical trapping agent such as dibutylhydroxytoluene or mono-t-butylhydroquinone (Patent Document 2: JP-A-9-511774), catalyst and crystalline layered layer Suppression technology using a combination with silicate (Patent Document 3: Japanese Patent Laid-Open No. 9-137196) and various decomposition suppression technologies using a combination of a catalyst and a clay mineral (Patent Document 4: Japanese Patent Laid-Open No. 9-025499) have been proposed. Yes.

  However, these techniques are insufficient to efficiently suppress damage to clothes and the like without producing coloring while exhibiting high bleaching power. That is, the suppression technique using a radical trapping agent is a technique that inactivates generated oxygen active species and suppresses damage and fading. On the other hand, this technique has a drawback that the object to be washed is colored by the radical trapping agent that has reacted with the oxygen active species. On the other hand, granulation with organic peracid precursors and bleach-activated catalysts using water-insoluble substances such as mineral substances, crystalline silicates, and viscous minerals keeps the distance from the object to be washed and physical contact opportunities. However, it is difficult to dissolve by the method of reducing the amount of the solution, the solubility is not sufficiently secured, and the sufficient bleaching effect may not be exhibited. In addition, the organic peracid precursor and the bleach activating catalyst are dissolved in the removal while they are not sufficiently dissolved and are in contact with the object to be washed for a long time. May occur, and the suppression effect is insufficient.

  On the other hand, metal complexes used for the catalyst generally have many compounds having absorption in the visible region, and usually have a color. Therefore, the subject that a to-be-washed | cleaned item is contaminated by a complex or a metal also exists. Moreover, the metal which does not form the complex which exists as an impurity in a metal complex, and the metal ion dissociated in the washing | cleaning liquid may cause a linear object contamination. Therefore, in order to blend the catalyst into the cleaning agent and put it into practical use, it is necessary to devise a technique that effectively exhibits the performance of the catalyst and at the same time does not cause damage or coloring.

Thus, when using a bleaching activation catalyst, the technique which prevents damage, such as discoloration of a to-be-washed object, embrittlement, and coloring, was desired.
Japanese Patent Laid-Open No. 6-057297 Japanese National Patent Publication No. 9-511774 JP-A-9-137196 Japanese Patent Laid-Open No. 9-25499 JP 2003-171697 A “Nature”, 1994, VOL. 369, p637-639 “J. Am. Chem. Soc.”, 1993, VOL. 115, p1772-1773

  The present invention has been made in view of the above circumstances, and is a bleached catalyst granulated product that has high solubility, exhibits high bleaching performance even in a short processing time, and can suppress dyeing to an object to be washed, and this It is an object of the present invention to provide a bleaching composition containing a granulated product.

  As a result of intensive studies to achieve the above object, the present inventor has determined that 1.0 mass of the transition metal that does not form a complex contained in the bleach activation catalyst in the granulated product is 1.0 mass relative to the bleach activation catalyst. % Or less to improve the solubility of the granulated product, and by diffusing it in the bleaching bath in a short time, the probability of direct contact with the object to be washed is reduced to suppress damage and the dissolution time As a result of shortening the length, it was found that high bleaching performance can be maintained even with less bleach-activated catalyst granules. In particular, the inventors have found that this effect is excellent by setting the bleach activation catalyst to a specific average particle size, and have achieved the present invention. In addition, when the bleach-activated catalyst granule of the present invention and a bleaching composition containing a peroxide that dissolves in water and generates hydrogen peroxide, the storage stability of the peroxide in the composition is obtained. It has been found that the property is improved, and the present invention has been made.

Therefore, the present invention
[1]. (A) Bleach activation catalyst having a transition metal complex structure 0.1 to 50% by mass
(B) Surfactant 0.1-50 mass%
(C) 10 to 90% by mass of the binder compound
The amount of transition metal that does not form a complex contained in the bleach activated catalyst in the granulated product is 1.0% by mass or less based on the bleach activated catalyst. A bleach-activated catalyst granulation, characterized in that
[2]. A bleaching composition comprising the bleach-activated catalyst granule according to [1] and a peroxide that dissolves in water to generate hydrogen peroxide.

  According to the present invention, a bleaching catalyst granulated product that has high solubility, exhibits high bleaching performance even in a short processing time, and can suppress dyeing to an object to be washed and the granulated product are contained. A bleaching composition can be provided.

Hereinafter, the present invention will be described in more detail.
The bleach activated catalyst granulated product of the present invention is
(A) 0.1-50% by mass of a bleach activation catalyst having a transition metal complex structure,
(B) Surfactant 0.1-50 mass%
(C) 10 to 90% by mass of the binder compound
The blending amount of the transition metal that does not form a complex contained in the bleaching activation catalyst in the granulated product is 1.0% by mass or less based on the bleaching activation catalyst.

  The component (A) of the present invention is a bleach activating catalyst having a transition metal complex structure, and acts as a catalyst in the bleaching solution, so that the bleaching effect continues to be expressed as long as the peroxide is present. High bleaching effect can be obtained with a small amount. The bleach activation catalyst of the present invention is composed of a transition metal atom such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum, and a ligand, a nitrogen atom or oxygen. A complex is formed through an atom or the like, and the transition metal contained is preferably cobalt, manganese or the like, and particularly preferably manganese.

  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 include chloride ions and ammonium ions.

  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. Etc.

  More specific ligands include carboxylate-containing amines, 1,4,7-trimethyl-1,4,7-triazacyclononane and similar compounds, porphins, porphyrins, phthalocyanines and their skeletons. Water-soluble or water-dispersible derivatives, 2,2′-dipyridyl derivatives, 1,10-phenanthroline derivatives, amines, tris (salicylideneiminoethyl) amine, N, N′-ethylenebis (4-hydroxysalicylidene) Minate), 13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11-benzotetraazacyclo Tridecine, 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6,6,2] hexadecane, 5,12-diethyl- , 5,8,12- tetraaza - bicyclo [6,6,2] hexadecane and the like. Specific bleach activation catalysts include carboxylate-containing cobaltamine, tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] penta. Fluorophosphate, 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 (Salicylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, 5,12-dimethyl-1,5,8,12-tetra Azabicyclo [6,6,2] hexadecane Ngan (II) chloride, [13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11- Benzotetraazacyclotridecine] -iron complex and the like. As a more preferable bleach activation catalyst in the present invention, tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphate , (Tris (salicylideneiminoethyl) amine) -manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, etc., with bleaching power and clothing damage and fading From the viewpoint, (tris (salicylideniminoethyl) amine) -manganese complex is preferable. In this invention, these can be used individually by 1 type or in combination of 2 or more types.

  (A) In the synthesis of a bleach-activated catalyst having a transition metal complex structure, a transition metal and a ligand are usually reacted. In this case, an unreacted transition metal remains as an impurity. In general, this transition metal is more reactive with hydrogen peroxide than the complexed metal, which can cause degradation of the hydrogen peroxide and decrease the bleaching effect or cause discoloration of the object to be washed. It reacts with hydrogen peroxide to produce active oxygen, which can cause damage to the washing object. Therefore, it is important to control the amount of transition metal that does not form a complex in the bleach activation catalyst. In this invention, it is necessary to make the compounding quantity of the transition metal which does not form the complex contained in the bleaching activation catalyst in a granulated material into 1.0 mass% or less with respect to a bleaching activation catalyst. The blending amount is preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less. Although the minimum of the compounding quantity of the transition metal which does not form a complex is not specifically limited, It is about 0.01 mass%. Since there is no change in the effect even if it is reduced below the lower limit, it may be economically disadvantageous to increase the purity of the complex more than necessary.

  Examples of a method for reducing the blending amount of the transition metal that does not form a complex to 1.0% by mass or less with respect to the bleach-activated catalyst include a synthetic method and a purification method.

Synthetic means The bleach-activated catalyst can be obtained by reacting a ligand with a transition metal. Usually, a transition metal salt having solubility in a solvent is used as the transition metal used in the synthesis. The molar ratio of the ligand to the transition metal salt during the reaction is usually 1: 1, and in this case, a transition metal that does not form a complex is generated. The molar ratio of ligand to transition metal (ligand / transition metal salt) is preferably adjusted to 100/90 to 100/98, transition metal salts that do not form a complex are reduced, and the concentration in the product is reduced. It can be made 1% or less. When the ratio is 100/99 to 100/100, the ratio of the fiber metal that does not form a complex often exceeds 1%. In addition, as a method of mixing the ligand and the transition metal salt, the ratio of the ligand is always increased by adding and mixing the transition metal salt solution little by little with respect to a large amount of the solution containing the ligand. Since it can be kept at a high state, it is more preferable as a means for suppressing a transition metal that does not form a complex.

Means by purification The purity of the obtained transition metal-ligand complex can be increased by purification. When the transition metal complex is a crystalline compound, crystallization is an effective means. The content of unreacted metal salt can be reduced by performing recrystallization by a conventional method using a solvent such as ethanol.

  The amount of transition metal that does not form a complex contained in the bleach activation catalyst can be measured using, for example, inductively coupled plasma analysis (IPC), high performance liquid chromatography (HPLC), an absorptiometer, and the like as follows. .

The total amount of transition metal and the amount of complex are measured by the following method, and the amount of transition metal that does not form a complex is calculated from the following formula.
Total transition metal amount (mol) -Amount of complex (mol)
= Amount of transition metal not forming a complex (mol)

[Measurement of total transition metal content]
The total amount of transition metal in the complex sample is analyzed by a conventional method using IPC. The amount of metal is determined by comparison with a standard sample of a predetermined transition metal.
[Measurement of complex amount]
Since the amount of the transition metal forming the complex coincides with the amount of the complex, it is obtained by quantifying the amount of the complex. In general, the amount of complex is determined by comparison with a standard sample using high performance liquid chromatography (HPLC), or by comparison with a standard sample of absorbance of ultraviolet absorption specific to the complex. In any analysis, a complex concentration in a sample is obtained by calculation from a calibration curve using a standard sample.

  The average particle size of the bleach-activated catalyst used for the bleach-activated catalyst granulated product has an important relationship with the solubility of the granulated product and the washing with the catalyst. When there are many components having a large average particle size, the solubility is lowered, and the chance that the catalyst molecules are in direct contact with the article to be washed increases, resulting in dyeing and damage. It is preferable that the average particle diameter of the bleaching activation catalyst contained in the granulated product is 5 to 40 μm, and the component having a particle diameter of 1 to 10 μm is 10% by mass or more of the whole. A more preferable range of the average particle diameter is 5 to 20 μm. A particularly preferable range is 5 to 15 μm. Further, the total particle size of 1 to 10 μm is preferably 20% by mass or more, and a particularly preferable range is 40% by mass or more.

  The average particle size and particle size distribution are measured using a particle size distribution measuring device (LDSA-3400A (17ch) manufactured by Tohnichi Computer Applications Co., Ltd.).

  The blending amount of the bleach activated catalyst having a complex structure of transition metal (A) in the granulated product of bleach activated catalyst is 0.1 to 50% by mass from the viewpoint of performance and damage to the washed object or fading. . The lower limit of the amount is preferably 1% by mass or more, more preferably 5% by mass or more, and the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

  The component (B) of the present invention is a surfactant and can be selected from any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Or 2 or more types can be used in appropriate combination. Specific examples thereof include polyoxyalkylene alkyl ether, olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, and mixtures thereof.

  The polyoxyalkylene alkyl ether preferably has an alkyl group having 12 to 20 carbon atoms, and an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO) is preferable. The average addition mole number is preferably 4 to 40, more preferably 20 to 30 in total in any case of EO, PO, or a mixture of EO and PO, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2.

  As the olefin sulfonate, sodium or potassium salt of α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms is preferable. The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms. As the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as sodium salt is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable. As a polyoxyethylene alkyl ether sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt having an alkyl group having 10 to 18 carbon atoms is preferable, and a sodium salt is particularly preferable. The average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is indicated by POE) is usually 1 to 10, preferably 1 to 5. In particular, sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5) and sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) are preferable. Any surfactant that is solid at room temperature is easy to use from the viewpoint of granulation.

  The blending amount of the surfactant (B) in the bleaching activated catalyst granulated product is 0.1 to 50% by mass from the viewpoint of solubility, damage to the washed object and fading. The lower limit of the amount is preferably 1% by mass or more, more preferably 5% by mass or more, and the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

  Component (C) of the present invention is a binder compound. As the binder compound, polyethylene glycol, a saturated fatty acid having 12 to 20 carbon atoms, a polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 or a salt thereof can be used. These can be used alone or in combination of two or more.

  The polyethylene glycol is preferably polyethylene glycol 1,000 to 20,000 (average molecular weight 500 to 25,000), more preferably average molecular weight 2,600 to 9,300, particularly preferably average molecular weight 5,000 to 9,000. 300.

  Moreover, as a C12-C20 saturated fatty acid, a C14-C20 thing is preferable, More preferably, it is a C14-C18 saturated fatty acid.

  In addition, the average molecular weight of the polyethylene glycol in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description. The weight average molecular weight of polyacrylic acid or a salt thereof is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.

  The blending amount of the (C) binder compound in the bleach-activated catalyst granulated product is 10 to 90% by mass from the viewpoint of productivity, shape retention, and dissolution time. The lower limit of the amount is preferably 20% by mass or more, more preferably 30% by mass or more, and the upper limit is preferably 85% by mass or less, more preferably 75% by mass or less.

  Bleach activated catalyst granules are water-insoluble or sparingly water-soluble, selected from powdered cellulose, silk powder, wool powder, nylon powder, and polyurethane powder as additives from the standpoint of improving manufacturability and suppressing damage to the wash. It is preferable to mix fiber powder. The water-insoluble or poorly water-soluble fiber powder here is a fiber powder having a solubility in 100 g of deionized water of 25 ° C. of less than 0.1 g, and the fiber is used as it is, frozen, or dispersed in a solvent. And pulverized and crushed using a pulverizer.

  Powdered cellulose refers to wood such as conifers and broadleaf trees, leaf fibers such as hemp, mitsumata, kouzo, ganpi, walla, bagasse, bamboo, stem fibers, gin leather fibers, seed hair fibers such as momen, kiwata and kapok. It is used after being refined, partially hydrolyzed if necessary, or using processed fibers such as cotton, hemp, rayon, etc., and has an amorphous part.

Natural fiber powder cellulose, silk powder and wool powder are preferred, powder cellulose and silk powder are more preferred, and powder cellulose is particularly preferred.
Specific examples of suitable water-insoluble or hardly water-soluble fiber powder in the present invention include KC Flock W-400G (manufactured by Nippon Paper Industries Co., Ltd.), Arbocel BE-600 / 10, Arbocel BE-00, Arbocel BE-600 / 30, Arbocel FD-600 / 30, Arbocel TF30HG, Arbocel WW-40, Arbocel BC-200, Arbocel BE-600 / 20 (manufactured by Rettenmeier), Idemitsu Petrochemical Co., Ltd. Idemitsu Silk Powder and Daito Kasei Kogyo Co., Ltd. silk powder And commercially available products such as 2002 EXDNATCOS Type-S manufactured by ElfAtochem.

  In the present invention, the size and length of the water-insoluble or poorly water-soluble fiber powder are not particularly limited, but the average particle diameter or the average fiber length is preferably 150 μm or less, preferably 100 μm or less. More preferably, in consideration of powdering at the time of production, 5 μm or more is preferable, and 10 μm or more is particularly preferable. Here, the measurement method of the average particle diameter and the average fiber length is not particularly limited, and for example, it is measured using a laser light scattering type particle size distribution measuring device or described in the Japanese Pharmacopoeia. It can be confirmed by calculating from the particle size distribution by sieving according to the particle size test, or by measuring by electron microscopy. The fiber powder of the above size may be selected from commercially available products within the above range, and may be pulverized or sieved to have the above size. . In this invention, it calculates from the particle size distribution by sieving according to the particle size test described in the Japanese Pharmacy Law.

  In addition, the water-insoluble or poorly water-soluble fiber powder may be used alone, or a plurality of water-insoluble or poorly water-soluble fiber powders may be mixed and used in an arbitrary ratio.

  In the present invention, when the water-insoluble or hardly water-soluble fiber powder is granulated together with the bleach-activated catalyst granulated product, the blending amount in the granulated product of the water-insoluble or hardly water-soluble fiber powder is 1 to 50% by mass. Is preferable, and 5-30 mass% is more preferable. If the above range is exceeded, granulation may be difficult or the strength of the granulated product may be reduced, and if it is less than the above range, the damage suppressing effect of the article to be washed may not be sufficiently suppressed.

Furthermore, it is also preferable to mix | blend radical trap agents, such as 4-methoxyphenol, from the point which improves the damage and discoloration prevention effect of clothing. In this case, the blending amount of the radical trapping agent is preferably 1% by mass or more and less than 10% by mass, more preferably 1 to 5% by mass in the bleach-activated catalyst granulated product.

  In addition, when preparing a granulated product or molded product by the extrusion granulation method described later, in order to improve the productivity by adjusting the viscosity, organic or inorganic such as sodium citrate, sodium sulfate, sodium tetraborate, etc. It is preferable to blend a salt and blend an aluminosilicate such as A-type zeolite as a grinding aid. The blending amount when blending these is preferably 3 to 50 mass%, more preferably 5 to 40 mass% in the bleach-activated catalyst granulated product.

  When blending pigments or dyes for the purpose of water-insoluble or sparingly water-soluble fiber powder, radical trapping agent, organic or inorganic salt, A-type zeolite, and aesthetics, (C) from the blending amount of the binder compound, the above components Reduce the amount of blending.

  The method for preparing the bleach-activated catalyst granulated product is not particularly limited, but examples of the granulating method include (A), (B), (C) components and optional components using a kneader and an extruder, After extruding into a noodle shape with a diameter of about 1 mm, pulverizing and granulating with a pulverizer, or dissolving and dispersing components (A) and (B) and optional components in the melted (C) component, cooling in a mixer There is a method of preparing a granulated product by pulverizing and granulating after preparing a lump by solidification.

  (C) It is preferable to add and melt | dissolve a component previously. In particular, it is preferable that the amount of water is minimized and the components to be melted are melted and added. (C) 40-100 degreeC is preferable, as for the melting temperature of a binder substance, More preferably, it is 50-90 degreeC, Most preferably, it is 50-80 degreeC. The components (A), (B), (C) and optional components are stirred and mixed until uniform, and then formulated into a normal granulator. Extrusion granulation can be mentioned as a preferable granulation method. Moreover, it is also preferable to set it as the tablet shape by a briquette machine.

  Add component (C) while fluidizing the mixture after mixing component (A) and component (B) using an agitation granulator, container rotary granulator, or fluidized bed granulator. Then, a granulation method can be used.

  The average particle diameter of the bleached activated catalyst granulated product is preferably 200 to 1,000 μm, particularly preferably 300 to 700 μm, from the viewpoints of solubility, stability and influence on the article to be washed. Below this range, the stability of the peroxide during storage is adversely affected and the risk of contaminating the item to be washed increases. On the other hand, if the amount exceeds this range, the solubility becomes poor and sufficient effects cannot be obtained, or damage may occur due to oxygen active species generated from a high concentration of catalyst on the object to be washed. The average particle size of the bleach-activated catalyst granulated product is obtained by calculating the particle size distribution using a sieve and calculating from the particle size distribution. The bulk density varies depending on the bulk density of the bleaching composition containing the bleach-activated catalyst granulated product, and is preferably within ± 0.3 g / mL of the bleaching composition from the viewpoint of classification, and usually 0.6 to 1. 1 g / mL is preferred. The angle of repose is optimally 60 ° or less, particularly 50 ° or less from the viewpoint of handleability.

  When the granulated product is blended with the bleaching composition, the bleach-activated catalyst granulated product is coated with a coating agent such as an oil-absorbing carrier, so that percarbonate, perborate, etc. in the composition are coated. The stability over time of the peroxide and the organic peracid precursor is improved, and the effect of suppressing damage is further enhanced by reducing direct contact with the object to be cleaned during dissolution.

  As the oil-absorbing carrier used as the coating agent, any oil-absorbing carrier particles can be used. Particles having a function as an oil-absorbing carrier tend to adhere to the granulated surface, which is preferable in production. Examples of the coating agent include A-type zeolite, P-type zeolite, white carbon, diatomaceous earth, and the like. Specifically, white carbon, A-type zeolite and the like are suitable. Considering the adhesion to the granulated product, the average particle size of the oil-absorbing carrier is preferably 10 to 100 μm.

  The mass ratio of the bleach activated catalyst granulated product to the coating agent is preferably 70/30 to 99.5 / 0.5 for the bleach activated catalyst granulated product / coating agent, more preferably 70/30 to 98/2. preferable. If the amount of the coating agent is small, the effect may not be exhibited. If the amount is too large, it may be excessively attached to the surface of the catalyst particles, and the probability of dropping off over time may increase.

  By thoroughly mixing the bleach activated catalyst granulated product and the coating agent, the coating agent adheres to the surface of the granulated product. As a coating method, any method can be used as long as it can mix the granulated product and the coating agent. Examples thereof include a method in which the granulated product and the coating agent are mixed with a ribbon mixer or a trommel. Moreover, it is preferable to remove the excess coating agent by separating it from the granulated product by sieving or the like.

  The present invention is a bleaching composition containing the above bleach-activated catalyst granulated product and a peroxide which dissolves in water and generates hydrogen peroxide, and preferably contains a surfactant. The bleaching composition of the present invention is also excellent in the storage stability of the peroxide in the composition.

  Here, the bleaching composition is a product that mainly removes stains on clothes and household products, and is defined as containing an oxygen bleach. Contaminations to be covered include stains on food and drinks, various stains such as stains on food and drinks, yellowing, darkening, and mold, and stains on shoes. As a treatment method, it is left for about several minutes to several hours or more than ten hours to one day, or added to a washing machine together with a detergent. For stains on tableware and long-use items, dissolve in a bowl and leave the tableware for more than 10 minutes to several hours or more than a dozen hours or add it to an automatic dishwasher. . Moreover, it can be used for dirt on a house and dirt on a washing machine.

  A bleaching composition for clothing is defined as a bleaching composition and a bleaching detergent composition. The difference between these is the bleaching composition that emphasizes bleaching power, compared to the bleaching composition. Thus, the bleaching detergent composition has a low blending amount of bleaching bases such as hydrogen peroxide, percarbonate, perborate and the like, and emphasizes detergency accordingly.

  Since the blending amount of the bleach-activated catalyst granulated product varies depending on the blending amount of the catalyst in the granulated product, the lower limit is 0.005% by mass or more in the bleaching composition in terms of the catalyst amount in the granulated product. More preferably, it is 0.01 mass% or more, Most preferably, it is 0.03 mass% or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or more.

  Specific examples of peroxides that dissolve in water to generate hydrogen peroxide include sodium percarbonate, sodium perborate, sodium perborate trihydrate, etc. From the viewpoint of stability at the time, it is preferable to use sodium percarbonate. In particular, sodium percarbonate is preferably coated sodium percarbonate in order to further improve the stability during storage. It is particularly preferable to coat with silicic acid and / or silicate and boric acid and / or borate. Specifically, as described in Japanese Patent No. 2,189,991 and the like, it is coated by spraying silicic acid and / or alkali metal silicate aqueous solution and boric acid and / or alkali metal borate aqueous solution. Further, it is preferable to use a material coated with a water-insoluble organic compound such as paraffin or wax, or powder blend with various inorganic materials such as sodium carbonate or sodium hydrogen carbonate for non-hazardous material. Furthermore, in the case of a bleaching composition containing a large amount of water in the composition due to the incorporation of a surfactant, particularly a bleaching detergent composition, it is preferable to use a coating peroxide with silicic acid and sodium borate as sodium percarbonate. More preferred. These peroxides can be used singly or in appropriate combination of two or more. As methods for producing coated sodium percarbonate, JP-A 59-196399, USP 4526698 (both sodium percarbonate coated with borate), JP-A-4-31498, JP-A-6-40709 The method published in the gazette and Unexamined-Japanese-Patent No. 7-11803 can also be mentioned. The average particle diameter of the inorganic peroxide is preferably 200 to 1,000 μm, more preferably 300 to 800 μm. In order to satisfy both solubility and stability, particles having a particle diameter of less than 125 μm and particles exceeding 1000 μm Is preferably 10% by mass or less in the peroxide which dissolves in water and generates hydrogen peroxide. Here, the average particle diameter can be confirmed by a method of obtaining a particle size distribution using a sieve and calculating from the particle size distribution. In the bleaching agent composition, considering the stability of the peroxide, the water content in the composition is preferably 2% by mass or less.

  The amount of the peroxide that dissolves in water and generates hydrogen peroxide is not particularly limited, but is preferably 20 to 90% by mass in the composition, more preferably a bleaching composition. Is 25 to 90 mass%, more preferably 30 to 90 mass%. Even if it exceeds the above range, the bleaching effect may not be enhanced against stain stains on clothing or yellowing stains on clothing that has been worn for a long time, and if less than the above range, sufficient bleaching effect against stubborn stains May not be obtained. If it is a bleaching detergent composition, 1 mass% or more and less than 20 mass% is preferable in a composition, More preferably, it is 2 mass% or more and less than 20 mass%. If the above range is exceeded, the bleaching effect on mild stains and the yellowing prevention effect of clothing may not increase any more. At the same time, if the above range is exceeded, a sufficient amount of surfactant cannot be secured and sufficient washing is performed. The effect may not be obtained. Moreover, if it is less than the said range, a bleaching effect may not be enough as a bleaching detergent composition.

  The amount of peroxide in the automatic dishwasher detergent is preferably 1% by mass or more and less than 20% by mass, more preferably 2% by mass or more and less than 20% by mass in the composition. As for the compounding quantity of the peroxide of a washing tub cleaner, 20-90 mass% is preferable in a composition, More preferably, it is 25-90 mass%, More preferably, it is 30-90 mass%.

  Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more. it can.

As an anionic surfactant, the following can be mentioned, for example.
(1) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms
(2) Alkane sulfonate having 10 to 20 carbon atoms (3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms
(4) C10-20 alkyl sulfate or alkenyl sulfate (AS)
(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 with 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 Mole-added alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms (7) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide Straight chain or branched chain alkyl having 10 to 20 carbon atoms in which 0.5 to 10 moles of an average of styrene and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) is added. Alkyl (or alkenyl) ether carboxylate having (or alkenyl) group (8) alkyl such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms Esters ether sulfate (9) saturated or unsaturated α- sulfofatty acid salts or methyl 8 to 20 carbon atoms, ethyl or propyl ester (alpha-SF or MES)
(10) Long chain monoalkyl, dialkyl or sesquialkyl phosphate (11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate (12) Higher fatty acid salt having 10 to 20 carbon atoms (soap)

  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, AES (for example, sodium or potassium salt) ), 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 was 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 (1) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ¹ CO (OA) _n OR ² (1)
(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 represents an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide and 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. R ² may have a substituent having 1 to 3 carbon atoms. A lower 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 (9) Fatty acid alkanolamide ( 10) Polyoxyethylene alkylamine (11) Alkyl glycoside (12) Alkylamine 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 (or alkenyl) ethers, fatty acid methyl esters and ethylene oxide Suitable examples include fatty acid methyl ester ethoxylates having added thereto, fatty acid methyl ester ethoxypropoxylates having ethylene oxide and propylene oxide added to fatty acid methyl esters, and the like. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types.

  Note that 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”, Kogyosho Co., Ltd., 1991). Year, 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 to 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 individually by 1 type or in combination of 2 or more types.

  In the case of a bleaching composition, the incorporation of a surfactant improves the solubility of hydrophobic components (such as perfumes) in the bleaching composition and the permeability to clothing. The lower limit of the blending amount is preferably 0.1% by mass or more, more preferably 0.2% by mass or more in the bleaching composition. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

  In the case of a bleaching detergent composition, the lower limit of the amount of the surfactant is preferably 10% by mass or more, more preferably 15% by mass or more in the bleaching detergent composition from the viewpoint of imparting sufficient cleaning performance. . The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less in the bleaching detergent composition. 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 detergents for automatic dishwashers, the lower limit of the amount of the surfactant is preferably 1% by mass or more in the detergent for automatic dishwashers from the viewpoint of ensuring sufficient cleaning performance and suppressing foaming. Preferably it is 3 mass% or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. In particular, polyoxyethylene polyoxypropylene alkyl ether is preferable as the surfactant for detergents for automatic dishwashers from the viewpoints of cleanability and foam control.

  In the case of a washing tub cleaner, the lower limit of the amount of the surfactant is preferably 3% by mass or more in the washing tub cleaner composition from the viewpoint of imparting sufficient cleaning performance. More preferably, it is 5 mass% or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.

  In the bleaching composition of the present invention, most of the surfactant to be blended in addition to the bleach-activated catalyst granule is preferably used as particles containing a surfactant. There are two types of particles containing a surfactant: a surfactant-containing particle having an anionic surfactant as a main surfactant and a surfactant-containing particle having a nonionic surfactant as a main surfactant. It can be roughly divided.

Surfactant-containing particles having an anionic surfactant as a main surfactant The surfactant-containing particles having an anionic surfactant as a main surfactant in the present invention are particles containing an anionic surfactant as an essential component. The particle | grains with the largest compounding quantity of an anionic surfactant among the surfactant components mix | blended in are meant. Therefore, other surfactants such as nonionic surfactants, cationic surfactants, and amphoteric surfactants other than anionic surfactants can be suitably blended although the blending amount is limited.

  The anionic surfactant used in the surfactant-containing particles having an anionic surfactant as a main surfactant is not particularly limited as long as it is used in the above-mentioned conventional detergents. Anionic surfactants can be used. In surfactant-containing particles having an anionic surfactant as a main surfactant, the surfactant is usually an anionic surfactant alone or a combination of two or more types, with the anionic surfactant as the main surfactant. Can be used.

  As the blending amount of all the surfactants in the surfactant-containing particles having an anionic surfactant as the main surfactant, 10 to 90 mass in the surfactant-containing particles from the viewpoint of providing sufficient cleaning performance. % Is preferable, more preferably 15 to 70% by mass, and still more preferably 15 to 50% by mass. The mass ratio of the anionic surfactant / other surfactant is preferably 100/0 to 50/50, more preferably 100/0 to 55/45, and further preferably 100/0 to 70/30. is there.

For the surfactant-containing particles having an anionic surfactant as the main surfactant, additives added to the bleaching composition described below can be used without any particular limitation.
Among these, examples of the inorganic builder include those having an effect of improving solubility, and potassium salts such as potassium carbonate and potassium sulfate, and alkali metal chlorides such as potassium chloride and sodium chloride. Of these, alkali metal chlorides such as potassium carbonate, potassium chloride, and sodium chloride are preferable from the viewpoint of the balance between the effect of improving solubility and cost.

  When potassium carbonate is blended, the blending amount is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 5 to 10% by mass in the surfactant-containing particles from the viewpoint of improving the solubility. %.

  When blending an alkali metal chloride, the blending amount is suitably 1 to 10% by mass, preferably 2 to 8% by mass, more preferably 3 to 3% in the surfactant-containing particles, from the viewpoint of improving the solubility. 7% by mass.

  The physical property value of the surfactant-containing particles in which the anionic surfactant is the main surfactant is not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1. 0.2 g / mL, more preferably 0.6 to 1.1 g / mL. The average particle size is preferably 200 to 1,500 μm, more preferably 300 to 1,000 μm. When the average particle size is less than 200 μm, dust may be easily generated, while when it exceeds 1,500 μm, the solubility may be insufficient.

  Furthermore, the fluidity of the surfactant-containing particles in which the anionic surfactant is the main surfactant is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If the angle of repose exceeds 60 °, the handleability of the particles may deteriorate.

Surfactant-containing particles having an anionic surfactant as a main surfactant can be obtained largely by the following two methods.
(1) Method of granulating neutralized salt type anionic surfactant (2) Method of granulating by dry neutralizing acid precursor of anionic surfactant

(1) The method of granulating a neutralized salt type anionic surfactant can be obtained by the following granulation method.
(1-1) Extrusion granulation method in which a raw material powder of a detergent component and a binder component (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, and then extruded and granulated, (1-2) kneading And then kneading and granulating the obtained solid detergent, (1-3) stirring granulation method of adding a binder component to the raw material powder and stirring and granulating with a stirring blade, (1-4) Rolling granulation method in which raw material powder is rolled and sprayed with a binder component to granulate, (1-5) Fluidized bed in which liquid binder is sprayed and granulated while fluidizing raw material powder. Examples thereof include a granulation method.

  (2) In the method of dry neutralizing the acid precursor of the anionic surfactant and granulating, the acid precursor of the anionic surfactant and the alkaline inorganic powder are neutralized while contacting and mixing, and granulation is performed. Basically, the granulation method used in (1) the method of granulating the neutralized salt type anionic surfactant is preferably used as well. Specific methods, apparatuses, conditions, etc. are as described above.

  Any suitable acid precursor of the anionic surfactant can be used as long as it is an acid precursor of the anionic surfactant that can be suitably used. Moreover, although it does not specifically limit as alkaline powder as a neutralizing agent, An alkali metal carbonate, an alkali metal silicate, an alkali metal phosphate, etc. are mentioned. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate / potassium, etc., and examples of the alkali metal silicate include sodium silicate, layered sodium silicate, and the like. Examples of the phosphate include sodium tripolyphosphate and sodium pyrophosphate. Among these, alkali metal carbonates are preferable, and sodium carbonate, potassium carbonate, and sodium carbonate / potassium are particularly preferable. These can use 1 type (s) or 2 or more types.

  Surfactant-containing particles containing an anionic surfactant granulated by the above-described method as a main surfactant may be classified as necessary, and only surfactant-containing particles having a desired particle size may be used in products. it can.

Surfactant-containing particles in which the nonionic surfactant is the main surfactant The surfactant-containing particles in which the nonionic surfactant is the main surfactant in the present invention includes a nonionic surfactant as an essential component. And the particle | grains with which the compounding quantity of nonionic surfactant is the largest among the surfactant components mix | blended in particle | grains are meant. Accordingly, other surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants other than nonionic surfactants can be blended although the blending amount is limited.

  The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and is not particularly limited as long as it is used in detergents as described above. Nonionic surfactants can be used. In addition, other surfactants such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can also be suitably used. The above surfactants can be used singly or in combination of two or more, and the nonionic surfactant is used as the main surfactant, and usually the nonionic surfactant alone or in combination of two or more. Use.

  In the surfactant-containing particles in which the nonionic surfactant is the main surfactant, the blending amount of all the surfactants is 5 to 70 mass in the surfactant-containing particles from the viewpoint of providing sufficient cleaning performance. %, Preferably 10 to 40% by mass. The ratio of nonionic surfactant / other surfactant is 100/0 to 50/50, preferably 100/0 to 60/40, and more preferably 95/5 to 70/30.

  Examples of other components contained in the surfactant-containing particles in which the nonionic surfactant is the main surfactant include inorganic and organic cleaning builders. As the cleaning builder, a cleaning builder that can be blended with the surfactant-containing particles having the above-mentioned anionic surfactant as the main surfactant can be used as well. The same applies to the preferred cleaning builder and the blending amount of the cleaning builder.

  In addition, in the surfactant-containing particles in which the nonionic surfactant is the main surfactant, an oil-absorbing carrier for supporting the nonionic surfactant, clay mineral as a granulating aid, and the like are blended. Is preferred.

  As the oil-absorbing carrier, an oil-absorbing substance having an oil absorption amount represented by the JIS-K5101 test method of preferably 80 mL / 100 g or more, preferably 150 to 600 mL / 100 g is suitably used. Examples of such an oil-absorbing carrier include components described in JP-A-5-125400 and JP-A-5-209200.

  These oil-absorbing carriers can be used singly or in appropriate combination of two or more. The oil-absorbing carrier is suitably 0.1 to 25% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 in the surfactant-containing particles in which the nonionic surfactant is the main surfactant. -15% by mass is contained.

  As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are particularly preferable. The clay mineral that can be preferably used as the detergent component of the present invention preferably has an oil absorption of less than 80 mL / 100 g, more preferably 30 to 70 mL / 100 g, and a bulk density of preferably 0.1 g / mL or more, particularly preferably 0.8. 2 to 1.5 g / mL. Specific examples of such clay minerals include components described in JP-A-9-87691.

  The clay mineral is contained in an amount of 0.1 to 30% by mass, preferably 0.5 to 20% by mass, particularly preferably 1 to 10% by mass in the surfactant-containing particles having a nonionic surfactant as a main surfactant. The

  In the surfactant-containing particles in which the nonionic surfactant used in the present invention is the main surfactant, additives described later can be blended without particular limitation, and the anionic surfactant and the main surfactant can be combined. Those that can be suitably blended in the surfactant-containing particles to be used can be similarly used.

  Although the physical property value of the surfactant-containing particles in which the nonionic surfactant is the main surfactant is not particularly limited, the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1. 0.2 g / mL, more preferably 0.6 to 1.1 g / mL. The average particle size is preferably 200 to 1,500 μm, more preferably 300 to 1,000 μm. When the average particle size is less than 200 μm, dust may be easily generated, while when it exceeds 1,500 μm, the solubility may be insufficient. Furthermore, the fluidity of the surfactant-containing particles in which the nonionic surfactant is the main surfactant is preferably 60 ° or less, particularly 50 ° or less as the angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

  Surfactant-containing particles in which the nonionic surfactant is the main surfactant can also be obtained by the same granulation method as the surfactant-containing particles in which the anionic surfactant is the main surfactant.

  It is preferable to mix | blend a phosphonic acid type chelating agent with the bleaching composition of this invention, It can use individually by 1 type or in combination of 2 or more types. By adding a phosphonic acid chelating agent, hydrogen peroxide is stabilized when the bleaching composition is dissolved in water, and contamination of the object to be washed by transition metals and catalyst complexes of impurities in the catalyst is suppressed. It is effective for.

  Examples of the phosphonic acid chelating agent include 1-hydroxyethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, and hydroxyethane-1,1. , 2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylene Phosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and salts thereof. Among them, 1-hydroxyethane-1,1-diphosphonic acid disodium (HEDP-2Na), 1-hydroxyethane-1,1-diphosphonic acid trisodium (HEDP-3Na), 1-hydroxyethane-1,1-diphosphonic acid Tetrasodium (HEDP-4Na) and sodium ethylenediaminetetra (methylenephosphonate) are preferred. Considering the influence on the bleaching power and the storage stability in the bleaching composition, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (HEDP-4Na) is more preferable.

  The lower limit of the blending amount of the phosphonic acid chelating agent is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more in the bleaching composition. The upper limit is preferably 10% by mass or less in the bleaching composition, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

In addition to the above components, various additives and the like can be blended in the bleaching composition of the present invention as necessary. These can be used individually by 1 type or in combination of 2 or more types. Although concretely shown below, each component may be described in duplicate.
(1) Detergency builders The following inorganic and organic detergency builders are mentioned.
(1) -1 Inorganic builder Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered silicic acid. Crystalline alkali metal silicate such as sodium (for example, trade name [Na-SKS-6] (δ-Na ₂ O · 2SiO ₂ ) of Clariant Japan), amorphous alkali metal silicate, sodium sulfate, potassium sulfate, etc. Sulfates, sodium chloride, alkali metal chlorides such as potassium chloride, orthophosphates, pyrophosphates, tripolyphosphates, phosphates such as metaphosphates, hexametaphosphates, phytates, crystalline aluminosilicates Of amorphous aluminosilicate, anhydrous silicic acid, sodium carbonate and amorphous alkali metal silicate Polymer (for example Rhodia under the trade name [NABION15]), and the like.

  Among inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, aluminosilicate, and anhydrous silicic acid are preferable.

  As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, but crystalline aluminosilicate is preferred from the viewpoint of cation exchange ability. As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be suitably blended, and the average primary particle size is preferably 0.1 to 10 μm. When blending crystalline aluminosilicate, the blending amount is preferably 1 to 40% by weight in the bleaching composition, and 2 to 30% by weight is particularly preferable from the viewpoint of powder physical properties such as washing performance and fluidity. .

  In the case of blending the crystalline alkali metal silicate, the blending amount is preferably 0.5 to 40% by weight, more preferably 1 to 25% by weight, and further preferably 3 to 3% in the bleaching composition from the viewpoint of cleaning performance. It is 20 mass%, Most preferably, it is 5-15 mass%.

  In the case where silicic anhydride is blended, the blending amount is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, particularly preferably 0.3 to 2% in the bleaching composition. % By mass. As an example of silicic anhydride, the product name Tokuseal Co., Ltd. Tokuyama etc. can be mentioned.

(1) -2 Organic Builder Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate. ; Hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate Salts; cyclocarboxylates such as pyromellitic acid salt, benzopolycarboxylate, and cyclopentanetetracarboxylate; carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate, etc. -Tercarboxylic acid salt; polyacrylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, polyacetal carboxylate such as polyglyoxylic acid, hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Acrylic acid polymers and copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid and the like; starch, cellulose, amylose, pectin And polysaccharide derivatives such as carboxymethyl cellulose.

  Among these organic builders, citrates, aminocarboxylates, polyacrylates, acrylic acid-maleic acid copolymers, and polyacetal carboxylates are preferred. In particular, hydroxyiminodisuccinate has a molecular weight of 1,000 to 80,000 acrylic acid-maleic acid copolymer salts, polyacrylates and molecular weights described in JP-A No. 54-52196 are 800 to 1,000,000, preferably 5,000. Polyacetal carboxylates, such as ˜200,000 polyglyoxylic acid are preferred. The blending amount of the organic builder is preferably 0.5 to 20% by mass in the bleaching composition, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.

  The detergency builder can be used singly or in appropriate combination of two or more. Organic builder such as citrate, aminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer, polyacetal carboxylate, etc. for the purpose of improving detergency and soil dispersibility in washing liquid It is preferable to use together with an inorganic builder such as zeolite. The amount of the builder is preferably 10 to 80% by mass and more preferably 20 to 75% by mass in the bleaching composition in order to impart sufficient detergency.

(2) pH adjuster The pH of the bleaching composition of the present invention is not particularly limited, but in order to obtain high bleaching power, the pH in a 1% by mass aqueous solution is 8 or more. It is preferable to adjust, and the pH in a 1% by mass aqueous solution is more preferably in the range of 9-11. Below this range, the bleaching effect may not be sufficient.

  As a technique for controlling pH, pH is usually adjusted with an alkali agent. In addition to the alkali agent described in the detergency builder, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, hydroxylation Sodium, potassium hydroxide, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of solubility in water and alkalinity, it is preferable to use NABION15 (manufactured by Rhodia), which is a mixture of sodium silicate and sodium carbonate and water in a ratio of 55/29/16.

  Moreover, in order to prevent that pH becomes high too much, it can also adjust to the said pH range using an acid etc. A metal scavenger can also be used as the acid. In addition, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid or their polycarboxylic acids, citric acid, sulfuric acid, hydrochloric acid and the like can be used. In addition, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from clothing stains during washing.

  The bleaching composition of the present invention may further contain a metal ion scavenger, a boron compound, and a phenolic radical trapping agent, if necessary, in order to enhance the bleaching effect and the effect of inhibiting clothing damage and fading.

(3) Metal ion scavenger The metal ion scavenger captures a trace amount of metal ions and exhibits the effect of increasing the stability of hydrogen peroxide during storage and the stability of hydrogen peroxide in the bleaching solution.

  As metal ion scavengers, in addition to those included in the above-mentioned phosphonic acid chelating agents and detergency builders, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid and salts thereof, diglycolic acid And organic acids such as citric acid, tartaric acid, oxalic acid and gluconic acid, and salts thereof.

  The compounding amount of the metal ion scavenger in the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.3 to 2% in the bleaching composition. % By mass. If the blending amount is less than 0.05% by mass, the stabilizing effect of the peroxide may not be sufficient, and if it exceeds 10% by mass, the stabilizing effect may not be enhanced. These metal ion scavengers can be used alone or in combination of two or more.

(4) Boron Compound The bleaching composition of the present invention further increases the bleaching effect by adding a boron compound, and the boron compound acts on hydrogen peroxide and free metal, so that the excess amount in the bleaching treatment solution is increased. The stability of hydrogen oxide can be further increased. Here, as the boron compound, compounds containing boron in the molecule, such as boric acid, sodium borate, potassium borate, ammonium borate, 4 sodium borate, 4 potassium borate, 4 ammonium borate, etc. are used. Among these, sodium tetraborate is particularly preferable and may be contained as a hydrate.

  When a boron compound is blended in the bleaching composition in the present invention, the blending amount is 20% by mass or less, more preferably 5% by mass or less in the bleaching composition. When mix | blending with a bleaching detergent composition, the compounding quantity is 15 mass% or less, More preferably, it is 3 mass% or less. Even if it exceeds the above range, it may be difficult to improve the bleaching effect and improve the stability of hydrogen peroxide. These boron compounds can be used singly or in appropriate combination of two or more.

(5) Phenolic radical trapping agent In the present invention, a phenolic radical trapping agent is further blended and used in combination with the above water-insoluble or poorly water-soluble fiber powder. Since coloring to clothing by the oxide of the system compound does not occur, it is more preferable. Examples of the phenol radical trapping agent include a compound having a phenolic hydroxyl group, an ester derivative of a phenolic hydroxyl group, an ether derivative, and the like.

  More specifically, as such a compound, cresol, thymol, chlorophenol, bromophenol, methoxyphenol, nitrophenol, hydroxybenzoic acid, salicylic acid, hydroxybenzenesulfonic acid, 2,6-ditertiarybutyl-p- Examples include cresol, naphthol, pyrogallol, phenoxyethanol and the like.

Among these, more preferred compounds include G.I. E. Penketh, J. et al. Appl. Chem. , Vol 7, pages 512 to 521 (1957), a compound having an oxidation-reduction potential (OP) ₀ (25 ° C.) of 1.25 V or less, more preferably a compound of 0.75 V or less. . Note that the lower limit of the oxidation-reduction potential (OP) ₀ (25 ° C.) is not particularly limited, but considering the influence on the bleaching effect, the normal oxidation-reduction potential (OP) The lower limit of ₀ (25 ° C.) is preferably about 0.60V. If the oxidation-reduction potential exceeds the above range, the stabilizing effect of hydrogen peroxide may not be sufficient. If the redox potential is too low, the bleaching power may be reduced.

  In addition, a radical trapping agent that dissolves quickly even with a small mechanical force as in the case of a bleaching treatment is more effective, and a logP value that is a hydrophobic parameter indicating solubility is particularly preferably 3 or less. . The hydrophobic parameter referred to here is generally used as a parameter indicating the property of the target compound. P (partition coefficient) in the log P value is expressed as P = Co / Cw as the ratio of the activity of the substance at equilibrium between water and octanol, where Co is the concentration in octanol and Cw is the water Concentration).

  Details of the hydrophobicity parameter are described in, for example, Science Special Issue No. 122 (1979), page 73. As a method for measuring the partition coefficient, a Flash Shaking method, a thin-layer chromatographic method, and a HPLC measuring method are known, but can also be calculated by calculation using parameters of Gose, Pitchett, Crippen et al. (J. Comp) Chem., 9, 80 (1998)).

  Among these compounds, 4-methoxyphenol and 4-hydroxybenzoic acid are particularly preferable in view of oxidation-reduction potential, solubility, and radical trapping agent stability when coexisting with peroxide. These phenolic radical trapping agents can be used singly or in appropriate combination of two or more.

  In the bleaching composition of the present invention, the phenolic radical trapping agent can be blended in any amount, but the preferred blending amount in the case of the bleaching composition is 0.001 to 13% by mass in the bleaching composition. Preferably in the range of 0.01 to 1% by mass, the preferred blending amount in the case of the bleaching detergent composition is 0.0001 to 1% by mass, more preferably 0.001 to 0.5% in the bleaching detergent composition. % By mass. If it is less than the above range, the combined use effect may not be sufficiently obtained, and if it exceeds the above range, the effect of damaging or fading the clothing may not increase any more, and coloring of clothing due to oxidation of the phenolic radical trapping agent may not occur. May occur.

(6) Fragrance As the fragrance, components described in JP-A Nos. 2002-146399 and 2003-89800 can be used. In addition, a fragrance | flavor composition is a mixture which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc. When mix | blending the said fragrance | flavor composition with the bleaching composition of this invention, the compounding quantity is 0.001-20 mass% in a bleaching composition, More preferably, it is 0.01-10 mass%.

  When blending the above fragrance components with the bleaching composition of the present invention, these fragrance components can be used by spraying the entire composition. Moreover, it can be used by impregnating the above-mentioned inorganic builder component. By impregnating, deterioration of the fragrance due to the peroxide is suppressed, and the impregnated fragrance is gradually released, so that a constant fragrance is maintained even after long-term storage.

(7) Dye Various dyes can be used to improve the appearance of the bleaching composition. Examples of the coloring matter used in the bleaching composition include dyes and pigments. Among them, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance such as oxides are particularly preferable. Preferred compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like. These dyes are preferably granulated together with the complex, and in this case, it is preferable to use those obtained by dissolving or dispersing the dye in a binder component such as polyethylene glycol (PEG). Further, as a bluish imparting agent, an aqueous solution or dispersion of a blue pigment such as ultramarine blue or a green pigment such as copper phthalocyanine is sprayed onto sodium sulfate or sodium carbonate for granulation, or a surfactant-containing particle or It can also be used by spraying on the bleaching composition of the invention.

  In addition, pigment water obtained by adding about 0.1 to 5% by mass of a dye to the polymer resin suspension to the spherical resin particles obtained by radical emulsion polymerization in an aqueous dispersion and heat-treating the resin resin suspension. The dispersion is also suitably used as an appearance imparting agent, like the bluing imparting agent.

  When the above-mentioned pigment component is blended with the bleaching composition of the present invention, the pigment is contained in the mixer with respect to the surfactant-containing particles or the finally obtained bleaching composition when preparing the above-mentioned surfactant-containing particles. The aqueous solution or aqueous dispersion of the components is preferably used by spraying or dripping, more preferably by spraying. Alternatively, the surfactant-containing particles or the finally obtained bleaching composition may be used by spraying or dripping an aqueous solution or aqueous dispersion of the dye component on the surface while being transported by a belt conveyor. More preferably it is used.

(8) Fluorescent whitening agent In the bleaching composition of the present invention, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-) is used as a fluorescent dye. 3-sulfostyryl) -biphenyl salts, 2- (styrylphenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, etc. It is done.

  Product names include Whitetex SA, Whiteex SKC (manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals), Lemonite CBUS- 3B (Khyati Chemicals) etc. can be contained. Among these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable, and the blending amount is preferably 0.001 to 1% by mass in the bleaching composition. These may be used alone or in combination of two or more.

(9) Enzymes Enzymes (enzymes that exert an enzymatic action in the washing step) include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified from the reactivity of the enzymes. Any can be applied to the present invention. Particularly preferred are protease, esterase, lipase, nuclease, cellulase, amylase and pectinase. Specific examples of protease are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promeline, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, etc. As commercially available products, sabinase, alcalase, cannase (manufactured by Novozymes), API21 (manufactured by Showa Denko KK), Maxacar, Maxabem (manufactured by Genencor), protease K-14 or 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, Lipex (manufactured by Novozymes), and liposum (manufactured by Showa Denko KK). Examples of cellulases include commercially available cellzymes (manufactured by Novozymes), cellulase described in claim 4 of JP-A 63-264699, and the like, and examples of amylases include commercially available Termamyl (manufactured by Novozymes). Can be mentioned. These enzymes can be used alone or in combination of two or more. In addition, it is preferable that the enzyme is granulated as separately stable particles and used in a state of being dry blended with the detergent dough (particles).

(10) Enzyme Stabilizer The bleaching composition of the present invention can contain calcium salt, magnesium salt, polyol, formic acid, boron compound and the like as an enzyme stabilizer. Among these, sodium tetraborate, calcium chloride and the like are more preferable, and the blending amount is preferably 0.05 to 2% by mass in the bleaching composition. These can be used individually by 1 type or in combination of 2 or more types.

(11) Other polymers The bleaching composition of the present invention has an average molecular weight of 200 to 200 in order to impart a recontamination preventing effect on hydrophobic fine particles as a binder or a powder physical agent when densifying. 200,000 polyethylene glycol, a polymer of acrylic acid and / or maleic acid having a weight average molecular weight of 1,000 to 100,000, cellulose derivatives such as polyvinyl alcohol, carboxymethyl cellulose, and the like can be blended. Moreover, vinylpyrrolidone etc. can be mix | blended in order to mix | blend the copolymer or terpolymer etc. of a terephthalic acid and ethylene glycol and / or a propylene glycol unit as a stain | pollution | release agent, and to provide a color transfer prevention effect. Among these, polyethylene glycol having an average molecular weight of 1,500 to 7,000 is preferable, and the blending amount is preferably 0.05 to 5% by mass in the bleaching composition. These can be used individually by 1 type or in combination of 2 or more types.

(12) Anti-caking agent As the anti-caking agent, paratoluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

(13) Antifoaming agent Examples of the antifoaming agent include those conventionally known as silicone / silica, and this antifoaming agent is described in JP-A-3-186307, page 4, which will be described below. It is good also as an antifoamer granulated material manufactured using the method as described in a lower left column. First, 20 g of Toray Dow Corning silicone (compound type, PS antifoam) is added to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nippon Star Chemical Co., Ltd. and mixed to obtain a homogeneous mixture. . Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of neutral anhydrous sodium sulfate at 70-80 ° C. were mixed, and then manufactured by Fuji Powder Co., Ltd. Granulate by an extrusion granulator (model EXKS-1) to obtain a granulated product.

(14) Organic peracid precursor An organic peracid precursor can be blended with the bleaching composition of the present invention. Organic peracids generated from organic peracid precursors have not only a bleaching effect but also a bactericidal effect in laundry systems, and also have the effect of reducing the number of living microorganisms remaining in clothing (Yoshitaka Miyamae, Akira Matsunaga, Tobe Seiichi, Kenji Takahashi, Haruo Yoshimura, Teruhisa Uzuki, 28th Symposium on Cleaning, p.157-p.165 (1996)).

  Therefore, a higher effect can be acquired by using together an organic peracid precursor and a bleaching activation catalyst from the point of disinfection effect. Specific examples of organic peracid precursors include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, undecanoyloxybenzene Sodium sulfonate, dodecanoyloxybenzene sodium sulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene Decanoyloxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene and the like.

（式中、Ｒ³はエステル基、アミド基又はエーテル基で分断されていてもよい炭素数１〜６、好ましくは１〜４、特に好ましくは１〜３のアルキル基であり、Ｒ⁸はエステル基、アミド基又はエーテル基で分断されていてもよく、ヒドロキシ基で置換されていてもよい炭素数１〜８、好ましくは２〜６のアルキレン基である。Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁹、Ｒ¹⁰はそれぞれ独立に炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくはメチル基、エチル基又はヒドロキシエチル基である。Ｘ^-は陰イオンであり、好ましくはハロゲンイオン、硫酸イオン、脂肪酸イオン又は炭素数１〜３のアルキル硫酸イオンである。） Moreover, the compound represented by the following general formula (2), (3) is also mentioned.

(In the formula, R ³ is an alkyl group having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, carbon atoms which may be separated by an ester group, an amide group or an ether group, and R ⁸ is an ester. R ⁴ , R ⁵ , R ⁶ , R ⁶ , R ⁵ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group, and X ⁻ is an anion, preferably a halogen atom. An ion, a sulfate ion, a fatty acid ion, or an alkyl sulfate ion having 1 to 3 carbon atoms.)

  From the viewpoint of sterilizing power, an organic peracid precursor that generates a C8 to C12 organic peracid is particularly preferable. Specific examples of these organic peracid precursors include decanoyloxybenzoic acid, sodium dodecanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, and the like. Among them, 4-decanoyloxy is preferred in terms of bleaching effect. Benzoic acid and sodium 4-nonanoyloxybenzenesulfonate are more preferred. From the viewpoint of the fading inhibiting effect, 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are preferable.

  In the present invention, the organic peracid precursor is preferably blended as a granulated product or a molded product. The blending amount of the organic peracid precursor in the granulated product or molded product is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the blending amount is outside this range, the effect of granulation may not be sufficiently obtained.

  The granulated product or molded product containing the organic peracid precursor is selected from polyethylene glycol, saturated fatty acids having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1,000 to 1,000,000 and salts thereof. It is preferable to formulate using a binder compound. The polyethylene glycol is preferably polyethylene glycol 1,000 to 20,000 (average molecular weight 500 to 25000), more preferably an average molecular weight 2,600 to 9,300, and particularly preferably an average molecular weight 7,300 to 9,300. Things are good. In addition, the saturated fatty acid having 12 to 20 carbon atoms is preferably a saturated fatty acid having 14 to 20 carbon atoms, and more preferably 14 to 18 carbon atoms. In addition, the average molecular weight of polyethyleneglycol here shows the average molecular weight of cosmetics raw material reference | standard (2nd edition comment) description. The weight average molecular weight of polyacrylic acid or a salt thereof is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance. Such a binder substance is used in the granulated product in an amount of 0.5 to 30% by mass, preferably 1 to 20% by mass, more preferably 5 to 20% by mass.

  In addition, in order to improve the solubility of the organic peracid precursor in the washing bath, a polyoxyalkylene alkyl ether, an olefin sulfonate, an alkylbenzene is added to the granulated product or molded product containing the organic peracid precursor. It is preferable to blend a sulfonate, an alkyl sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt, or a mixture thereof. The blending amount is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass in the granulated or molded product containing the organic peracid precursor.

  The polyoxyalkylene alkyl ether preferably has an alkyl group having 10 to 15 carbon atoms, and is preferably an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). The average addition mole number is preferably 4 to 30, more preferably 5 to 15 in total in any case of EO, PO, or a mixture of EO and PO, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2.

  The olefin sulfonate is preferably a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms. The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group. Further, as the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as sodium salt is preferable, and sodium lauryl sulfate ester or myristyl sulfate ester sodium is particularly preferable. Moreover, as a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C18 alkyl group is preferable, and a sodium salt is favorable. Here, the average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is represented by POE) is 1 to 10, preferably 1 to 5, and particularly sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5). ), Sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) is good.

  The bleaching composition of the present invention can be obtained by mixing a bleach-activated catalyst granulated product, a peroxide that dissolves in water and generates hydrogen peroxide, and the above-mentioned optional components.

  Although the physical property value of the finally obtained bleaching composition is not particularly limited, the bulk density is usually 0.3 g / mL or more, preferably 0.4 to 1.2 g / mL, more preferably. Is 0.5 to 1.0 g / mL. The average particle size is preferably 200 to 1,500 μm, more preferably 300 to 1,000 μm. When the thickness is less than 200 μm, dust may be easily generated. On the other hand, when the thickness exceeds 1,500 μm, the solubility may be insufficient. Furthermore, the fluidity of the bleaching composition is preferably 60 ° or less, particularly 50 ° or less as the angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate. The bulk density of the bleach-activated catalyst granule, the surfactant particle and the bleaching composition of the present invention is measured according to JIS K3362, and the angle of repose is formed when particles filled in the container flow out. Measure the angle between the slip plane and the horizontal plane. The angle of repose is measured by the so-called discharge method.

  The bleaching composition of the present invention is not particularly limited in its washable and usage methods. For example, textile products such as clothes, cloths, sheets and curtains, paper products such as wood pulp, tableware and glass, laundry By using it on hard surfaces such as tanks in the same manner as ordinary bleaching detergent compositions, organic stains, yellowing substances, stains, molds and the like can be bleached and removed.

  The bleaching composition of the present invention can be suitably used particularly for applications / purposes such as removal of food stains or yellowing, suppression of discoloration of colored pattern fibers, disinfection of fibers, and suppression of malodor generation in room drying. In addition, as a cleaning composition for clothes, washing of washing tub, suppression of mold generation, cleaning composition for automatic dishwashing machine, disinfection in automatic dishwashing machine cabinet, suppression of mold generation, deodorization, etc. It can also be suitably used for purposes / purposes.

  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. In the following examples, unless otherwise specified, the composition “%” is mass%, the amount of each component in the table is the pure component for the composition of the surfactant-containing particles in Table 3 and Table 4. The other amounts are shown in terms of the amount as they are.

[Preparation Examples A1 to A4]
Preparation of Bleach Activation Catalyst Having Transition Metal Complex Structure Bleach activation catalysts A1 to A4 shown in Table 1 were obtained.
As the catalyst compound, a (tris (salicylideniminoethyl) amine) -manganese complex represented by the following formula was used.

材料としてトリス（２−アミノエチル）アミン（東京化成工業（株）製 試薬）、サリチルアルデヒド（東京化成工業（株）製 試薬）、塩化マンガン４水和物（関東化学（株）製 試薬）、メタノール（関東化学（株）製 試薬）、エタノール（甘糟化学産業（株）製 試薬）を用い以下の方法で合成を行なった。
トリス（２−アミノエチル）アミン４８．７ｇ（０．３３３ｍｏｌ）を反応容器に入れ、メタノール３００ｍＬで溶解し、０℃に冷却した。これにサリチルアルデヒド１２１．９ｇ（０．９９８ｍｏｌ）をメタノール１００ｍＬで溶解した液を１時間かけて滴下した。滴下終了後さらに０℃で１時間撹拌した。撹拌終了後、０℃で時間放置後、析出した黄色の結晶を桐山ロートで熱時ろ過した。
得られた結晶を５００ｍＬのエタノールで際結晶を行ない精製トリス（サリチリデンイミノエチル）アミンを１４３ｇを得た。
精製トリス（サリチリデンイミノエチル）アミン１００ｇを０．２ｍｍｏｌをエタノール５Ｌに溶解し、この溶液に塩化マンガン・４水和物０．１８ｍｍｏｌを室温下で添加した。室温で３時間撹拌後、原圧下でエタノールが約８００ｍＬになるまでの濃縮した。
さらにエタノール溶液を加熱還流し、熱時ろ過後、ろ液を熱時ろ過し再結晶を行なった。この操作を２回繰り返し、純度１００％のサンプルを得た。錯体の純度は、錯体サンプル中の全Ｍｎ量（Ａ）を、ＩＰＣを用いた分析により測定した。錯体量の定量（Ｂ）には、高速液体クロマトグラフィー（ＨＰＬＣ）を用い、これらＡ，Ｂの値より純度１００％であることを確認した。

As materials, tris (2-aminoethyl) amine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), salicylaldehyde (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), manganese chloride tetrahydrate (a reagent manufactured by Kanto Chemical Co., Inc.), Synthesis was carried out by the following method using methanol (a reagent manufactured by Kanto Chemical Co., Inc.) and ethanol (a reagent manufactured by Kansu Chemical Industry Co., Ltd.).
48.7 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 prepared 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 time, and the precipitated yellow crystals were filtered with a Kiriyama funnel while hot.
The obtained crystals were crystallized with 500 mL of ethanol to obtain 143 g of purified tris (salicylideniminoethyl) amine.
0.2 mmol of 100 g of purified tris (salicylideniminoethyl) amine was dissolved in 5 L of ethanol, and 0.18 mmol of manganese chloride tetrahydrate was added to this solution at room temperature. After stirring at room temperature for 3 hours, ethanol was concentrated to about 800 mL under the original pressure.
Further, the ethanol solution was heated to reflux and filtered while hot, and then the filtrate was filtered while hot for recrystallization. This operation was repeated twice to obtain a sample having a purity of 100%. The purity of the complex was measured by analyzing the total amount of Mn (A) in the complex sample using IPC. For quantitative determination (B) of the complex amount, high-performance liquid chromatography (HPLC) was used, and it was confirmed that the purity was 100% from these A and B values.

  30 g of the sample having a purity of 100% was pulverized with a pulverizer (Wonder Crush mill) and pulverized so that the average particle size was about 30 μm. The component of 1-10 micrometers in that case was 12 mass%. Similarly, it grind | pulverized so that an average particle diameter might be set to 15 micrometers and 10 micrometers. The components of 1 to 10 μm at that time were 29% by mass and 50% by mass, respectively. The average particle size was adjusted according to the time taken for the pulverizer.

  The average particle size and particle size distribution were measured using a particle size distribution measuring device (LDSA-3400A (17ch) manufactured by Tohnichi Computer Applications Co., Ltd.). Furthermore, a predetermined amount of manganese chloride (impurity Mn) was added to 20 g of the above average particle diameter to prepare bleaching activation catalysts A-1 to A-4. For example, in the case of A-1, 23 mg of manganese chloride is added to 20 g of the catalyst pulverized product.

In addition, the compounding quantity of the transition metal which does not form a complex was measured with the following method.
The amount of Mn genus contained in the bleach activation catalyst was measured by a conventional method using inductively coupled plasma analysis (IPC). The complex amount was determined by dissolving the complex sample in DMSO (dimethyl sulfoxide) or DMF (dimethylformamide), measuring the absorbance at 590 nm, and comparing the purity with a standard sample. The total amount of transition metal and the amount of complex were measured by the following method, and the amount of transition metal not forming a complex was calculated from the following formula.
Total transition metal amount (mol) -Amount of complex (mol)
= Amount of transition metal not forming a complex (mol)

Preparation Example of Bleach Activated Catalyst Granules Bleach activated catalyst granulated materials 1 to 7 listed in Table 2 were obtained by the following method.
For the granulated products 1 to 3, melted polyethylene glycol (PEG 6000) and other components were uniformly mixed at 70 ° C. using a kneader, and then cooled to room temperature (20 ° C.) with stirring. A solid of ˜5 cm was obtained. Next, the solid material was pulverized and granulated with a pulverizer to prepare a granulated material having an average particle size shown in Table 2.
For granulated products 4-7, all the components of the composition shown in Table 2 were uniformly mixed, put into Extrude Ohmic EM-6 manufactured by Hosokawa Micron, kneaded and extruded, and then cut with a cutter Thus, a pellet-shaped molded article <1> having a diameter of 0.8 mmφ and a length of 0.5 to 1 mm was obtained (kneading temperature 60 ° C., temperature after extrusion and cutting 20 ° C.).
Next, the molded product <1> was introduced into a Fitzmill DKA-3 type manufactured by Hosokawa Micron Corporation and pulverized to prepare a granulated product <2> having an average particle diameter shown in Table 2.

[Measurement of average particle size]
The bleaching-activated catalyst granulated product is classified using a 9-stage sieve having a mesh opening of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 149 μm and a tray. I did it. In the classification operation, a sieve with a small opening is stacked in the order of a sieve with a large opening, and a bleaching activated catalyst granule sample of 100 g / times is placed on the top of the top 1,680 μm sieve, and the lid is capped. Mounted on a low tap type sieve shaker (manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), and shaken for 10 minutes. It collect | recovered for every eye and measured the mass of the sample.
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 diameter (mass 50%) was calculated from 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.

The components in Table 2 are shown.
AOS-Na: α-olefin sulfonate sodium having 14 carbon atoms (manufactured by Lion Corporation, Lipolane PJ-400)
AS-Na: sodium lauryl sulfate (manufactured by Nikko Chemicals, SLS, pure AS-Na 95.7%)
Nonionic surfactant 3: Polyoxyethylene lauryl ether-1: EO25 EMALEX 725 manufactured by Nippon Emulsion Co., Ltd. Nonionic surfactant 4: Polyoxyethylene stearyl ether-2: EO20 EMALEX 620 manufactured by Nippon Emulsion Co., Ltd. PEG6000: Polyethylene Glycol (manufactured by Lion Corporation, trade name: PEG # 6000M)
・ Cellulose powder: Product name: Arbocel FD600 / 30, manufactured by Rettenmeier ・ Zeolite A: Type A zeolite (manufactured by Mizusawa Chemical Co., Ltd.)
・ White carbon: Silica fine powder (Tokuyama, Tokuyama Co., Ltd.)

Surfactant-containing particle groups 1 to 12 described in Tables 3 and 4 were obtained.
Production method of surfactant-containing particle group 1 According to the composition shown in Table 3 below, surfactant-containing particle group 1 was 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. A surfactant excluding α-SF-Na (α-sulfo fatty acid methyl ester sodium) and a nonionic surfactant and polyethylene glycol (PEG 6000) were added thereto, followed by stirring for 10 minutes. Subsequently, the polymer and the optical brightener were added, and after stirring for another 10 minutes, a part of the powder A-type zeolite (zeolite A) (2.0% equivalent amount (vs. each particle group, the same applies hereinafter)) was mixed. A-type zeolite for occasional addition, A-type zeolite for grinding aid equivalent to 3.2%, A-type zeolite for surface coating equivalent to 1.5%), sodium carbonate and potassium carbonate were added. The slurry is further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray-dried under the condition of a hot air temperature of 280 ° C. using a countercurrent spray drying tower, and the average particle size is 320 μm, the bulk density is 0.00. A spray-dried particle of 30 g / mL and 5% moisture (105 ° C., reduced amount for 2 hours, the same applies hereinafter) was obtained.

  On the other hand, an α-sulfo fatty acid methyl ester sodium aqueous slurry (moisture concentration of 25%) obtained by sulfonating and neutralizing the starting fatty acid ester is partially mixed with a nonionic surfactant (α-sulfo fatty acid methyl ester sodium). 25%) was added and concentrated under reduced pressure with a thin-film dryer until the water content was 11% to obtain a mixed concentrate of sodium α-sulfo fatty acid methyl ester and a nonionic surfactant.

  A continuous kneader (Kurimoto Co., Ltd.) was prepared by mixing the dried particles described above, this mixed concentrate, 2.0% equivalent of A-type zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition. (Kakosho, KRC-S4 type) was kneaded under conditions of a kneading capacity of 120 kg / h 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 using a pelleter double equipped with a die having a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) (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) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolled for 1 minute while spraying with 0.5% equivalent of nonionic surfactant and perfume, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Surface modification was carried out to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, the surfactant-containing particles are transferred on the belt conveyor at a speed of 0.5 m / s (the layer height of the surfactant-containing particles on the belt conveyor). 30 mm, layer width 300 mm), and a 20% aqueous dispersion of the dye was sprayed on the surface thereof to obtain a surfactant-containing particle group 1 (average particle size 550 μm, bulk density 0.84 g / mL).

Production method of surfactant-containing particle group 2 According to the composition shown in Table 3 below, surfactant-containing particle group 2 was 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 were added α-SF-Na (α-sulfo fatty acid methyl ester sodium) and a surfactant other than nonionic surfactant and polyethylene glycol, and the mixture was stirred for 10 minutes. Subsequently, acrylic acid / maleic acid copolymer sodium (Polymer A), HIDS, and optical brightener were added, and the mixture was further stirred for 10 minutes, and then a part of the powder A-type zeolite (7.0% equivalent amount) Add A-type zeolite for mild addition, excluding A-type zeolite for grinding aid equivalent to 3.2%, A-type zeolite for surface coating equivalent to 1.5%), sodium carbonate, potassium carbonate added did. The slurry is further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray-dried under the condition of a hot air temperature of 280 ° C. using a counter-current spray drying tower to obtain an average particle size of 290 μm, a bulk density of 0. Spray-dried particles of 32 g / mL and 5% moisture were obtained.

  On the other hand, an α-sulfo fatty acid methyl ester sodium aqueous slurry (moisture concentration of 25%) obtained by sulfonating and neutralizing the starting fatty acid ester is partially mixed with a nonionic surfactant (α-sulfo fatty acid methyl ester sodium). 25%) was added and concentrated under reduced pressure with a thin-film dryer until the water content was 11% to obtain a mixed concentrate of sodium α-sulfo fatty acid methyl ester and a nonionic surfactant.

  A continuous kneader (Kurimoto Co., Ltd.) was prepared by mixing the above-mentioned dry particles, this mixed concentrate, 7.0% equivalent amount of A-type zeolite, 0.5% equivalent amount of the remaining nonionic surfactant and water except for spray addition. (Kakosho, KRC-S4 type) was kneaded under conditions of a kneading capacity of 120 kg / h 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 using a pelleter double equipped with a die having a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) (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) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolled for 1 minute while spraying with 0.5% equivalent of nonionic surfactant and perfume, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Surface modification was carried out to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of the dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 2 (average particle) Diameter 550 μm, bulk density 0.86 g / mL).

Production Method of Surfactant-Containing Particle Group 3 Of the compositions shown in Table 3 below, nonionic surfactant, A-type zeolite for 2.0% equivalent addition during kneading, 3.2% equivalent for grinding aid A slurry with a water content of 38% was prepared by dissolving or dispersing components other than A-type zeolite for surface coating, 1.5% equivalent amount of surface-coated zeolite, pigments and fragrances in water, followed by countercurrent spray drying. Spray drying was performed using a tower at a hot air temperature of 300 ° C. to obtain spray-dried particles having an average particle size of 330 μm, a bulk density of 0.30 g / mL, and a moisture content of 3%. Along with these dry particles, a 2.0% equivalent amount of A-type zeolite, a 0.5% equivalent amount of nonionic surfactant except for spray addition and water were continuously kneaded (KRC-S4, KRC-S4). And kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product.

  This surfactant-containing kneaded product was cut with a cutter while extruding it using a pelleter double equipped with a die having a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) (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) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Rolled for 1 minute while spraying with 0.5% equivalent of nonionic surfactant and perfume, adding 1.5% equivalent of fine powder A-type zeolite under the conditions of rate 30 volume%, rotation speed 22rpm, 25 ° C Surface modification was carried out to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of the dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 3 (average particle) Diameter 540 μm, bulk density 0.77 g / mL).

Production method of surfactant-containing particle group 4 According to the composition shown in Table 3 below, surfactant-containing particle group 4 was 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 50 ° C. Sodium sulfate and a fluorescent brightening agent were added thereto and stirred for 10 minutes. Subsequently, after adding sodium carbonate, sodium salt of acrylic acid / maleic acid copolymer and ASDA were added, and further stirred for 10 minutes, and then sodium chloride and a part of powder A-type zeolite were added. The slurry was further stirred for 30 minutes to prepare a slurry for spray drying.

  The temperature of the obtained slurry for spray drying was 50 ° C. This slurry was spray-dried with a countercurrent spray dryer equipped with a pressure spray nozzle to obtain spray-dried particles having a moisture content of 3%, a bulk density of 0.50 g / mL, and an average particle size of 250 μm.

  Separately, nonionic surfactant, polyethylene glycol, anionic surfactant (LAS-Na, AS-Na, α-SF-Na and soap) are mixed at a temperature of 80 ° C., and the water content is 10 mass. % Surfactant composition was prepared. LAS-Na was used as a solution neutralized with an aqueous sodium hydroxide solution.

  Then, the obtained spray-dried particles are put into a Roedige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a blade-shaped excavator and having a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume). The stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started while flowing 80 ° C. warm water through the jacket at a flow rate of 10 L / min. The surfactant composition prepared above was added thereto over 2 minutes and then stirred for 5 minutes, and then a layered silicate (SKS-6, average particle size 5 μm) and a part of the powder A-type zeolite (10 % Equivalent amount) and stirred for 2 minutes to obtain surfactant-containing particles.

  In order to color a part of the surfactant-containing particles after mixing the obtained surfactant-containing particles and a part of powder A-type zeolite (equivalent to 2%) with a V blender and spraying a fragrance, A 20% aqueous dispersion of the dye was sprayed in the same manner as in the surfactant-containing particle group 1 to obtain a surfactant-containing particle group 4 (average particle size 300 μm, bulk density 0.75 g / mL).

Production method of surfactant-containing particle group 5 Among the compositions shown in Table 3 below , components other than 5.0% equivalent amount of surface-coated A-type zeolite, polyethylene glycol, layered silicate, pigment and fragrance are used in water. After preparing a dissolved or dispersed slurry with a water content of 38%, it is spray-dried using a countercurrent spray drying tower at a hot air temperature of 300 ° C., an average particle size of 320 μm, a bulk density of 0.36 g / mL, and a water content of 3 % Spray-dried particles were obtained. This spray-dried particle is equipped with a blade-shaped excavator, and the excavator-wall clearance is 5 mm and is loaded into a Ladige mixer (M20 type, manufactured by Matsubo Co., Ltd.) (filling rate 50% by volume), spindle 200 rpm, chopper Stirring at 200 rpm was started. After 30 seconds from the start of stirring, polyethylene glycol and water heated to 60 ° C. were added in 2 minutes, and stirring granulation was continued under the condition of a jacket temperature of 30 ° C. until the average particle size became 400 μm.

Finally, layered silicate (SKS-6, average particle size 5 μm) and 5.0% equivalent amount of finely divided A-type zeolite were added, stirred for 1 minute, surface-modified, sprayed with fragrance, and surfactant-containing particles Got.
In order to color a part of the obtained surfactant-containing particles, the surfactant-containing particles are transferred on the belt conveyor at a speed of 0.5 m / s (the layer height of the surfactant-containing particles on the belt conveyor). 30 mm, layer width 300 mm) A 20% aqueous dispersion of the dye was sprayed on the surface to obtain a surfactant-containing particle group 5 (average particle size 400 μm, bulk density 0.78 g / mL).

Production method of surfactant-containing particle group 6 According to the composition shown in Table 3 below, surfactant-containing particle group 6 was 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. After preparing a slurry with a water content of 38% in which components other than A-type zeolite, sodium carbonate, pigment and flavor are dissolved or dispersed in water, the slurry is spray dried using a countercurrent spray drying tower at a hot air temperature of 300 ° C. Spray-dried particles having an average particle diameter of 280 μm, a bulk density of 0.32 g / mL, and a water content of 6% were obtained.

  Filled with a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum inner wall surface of the container 131.7 L and two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Fine powder A-type zeolite and sodium carbonate were added under the conditions of a rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and the surface was modified by rolling for 1 minute while spraying a fragrance to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 6 (average particle) Diameter 350 μm, bulk density 0.48 g / mL).

Production method of surfactant-containing particle group 7 According to the composition shown in Table 3 below, surfactant-containing particle group 7 was produced in the same procedure as the method of producing surfactant-containing particle group 6, and surfactant-containing particles Group 7 (average particle size 350 μm, bulk density 0.50 g / mL) was obtained.

Production method of surfactant-containing particle group 8 Among the compositions shown in Table 3 below, all raw materials except surfactant, 5.0% equivalent amount of P-type zeolite (zeolite B), pigment, and fragrance used for surface coating (Temperature 25 ° C.) equipped with a blade-shaped excavator, charged into a Ladige mixer (M20 type, manufactured by Matsubo Co., Ltd.) having a clearance between the shovel and the wall surface of 5 mm (filling rate 50% by volume), spindle 200 rpm, Chopper 200 rpm stirring was started. 30 seconds after the start of stirring, a surfactant mixture (nonionic surfactant and anionic surfactant preheated to 60 ° C. and uniformly mixed) and water (temperature 60 ° C.) were added in 2 minutes, jacket temperature Agitation granulation was continued at 30 ° C. until the average particle size reached 400 μm. Finally, 5.0% equivalent amount of P-type zeolite (zeolite B) was added, stirred for 30 seconds, surface-modified and sprayed with a fragrance to obtain surfactant-containing particles.
In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 8 (average particle) 400 μm in diameter and 0.80 g / mL bulk density) were obtained.

Production method of surfactant-containing particle group 9 Among the compositions shown in Table 4 below, fluorescent whitening agent, potassium carbonate and sodium carbonate pulverized product (sodium carbonate is a tabletop fine pulverizer (stud mill 63C type, manufactured by Alpine) The powder material (excluding the coating agent) containing the powder, which has been pulverized to an average particle diameter of 30 μm) in a fluidized bed (made by Paulex, Glatt-POWREX, model number FD-WRT-20). Mass was added so that the layer thickness was 200 mm. Thereafter, 20 ° C. wind (air) is sent into the fluidized bed, and after confirming that the powder is fluidized, α-SF-H (α-sulfo fatty acid alkyl ester) is directed toward the fluidized powder layer. Sprayed from the top. The granulation operation was performed while adjusting the fluid velocity in the fluidized bed within the range of 0.2 to 2.0 m / s while confirming the fluidized state.
α-SF-H was sprayed at 60 ° C., and a two-fluid hollow cone nozzle with a spray angle of 70 ° was used as the nozzle for spraying. The spray rate was about 400 g / min. After spraying of α-SF-H, a 20 ° C. wind (air) was further fed into the fluidized bed and aged for 240 seconds. Further, the granulated material is discharged from the fluidized bed, and within a rolling drum (diameter 0.6 m, length 0.48 m, thickness 1 mm × width 12 cm × length 48 cm with baffle plates, rotation speed 20 rpm) An amount equivalent to 4.5% of type A zeolite was coated.
Thereafter, a 35% hydrogen peroxide aqueous solution (4.7% particles) was added to the obtained particles as a rolling drum (diameter 0.6 m, length 0.48 m, thickness 1 mm × width 12 cm × length 48 cm). After spraying within 4 sheets and rotating at 20 rpm), for the purpose of improving fluidity, an amount equivalent to 5.0% of A-type zeolite was further coated and a fragrance was sprayed.
In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 9 (average particle) Diameter 380 μm, bulk density 0.50 g / mL).

Production Method of Surfactant-Containing Particle Group 10 Of the compositions shown in Table 4 below, A-type zeolite for nonionic surfactant, 4.2% equivalent amount of grinding aid and 2.0% equivalent amount of surface coating After preparing a slurry of 40% water in which ingredients other than montmorillonite, white carbon, pigment and fragrance were dissolved or dispersed in water, the slurry was spray-dried at a hot air temperature of 300 ° C. using a countercurrent spray drying tower and averaged Spray-dried particles having a particle diameter of 300 μm, a bulk density of 0.45 g / mL, and a water content of 3% were obtained. Along with these dry particles, montmorillonite, white carbon, nonionic surfactant and water were put into a continuous kneader (manufactured by Kurimoto Steel Works, KRC-S4 type), and the conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. To obtain a surfactant-containing kneaded product.

  This surfactant-containing kneaded product was cut with a cutter while extruding it using a pelleter double equipped with a die having a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) (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, 4.2% 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 the product was cooled under cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 8 mm / 6 mm / 3 mm, number of rotations) Fitzmill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) : All stages 3760 rpm). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7L with two baffle plates with clearance of 20 mm from inner wall surface and height of 45 mm) An amount equivalent to 2.0% of fine powder A-type zeolite was added under the conditions of a rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., rolled for 2 minutes, surface-modified, and sprayed with a fragrance.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 10 (average particle) Diameter 560 μm, bulk density 0.80 g / mL).

Production method of surfactant-containing particle group 11 Among the compositions shown in Table 4 below, powder raw materials such as sodium carbonate, A-type zeolite excluding post-addition, STPP and the like are put into a mixer, and then a stirring blade and a chopper are placed. After starting, add a mixture of fluorescent brightener and acid precursor of anionic surfactant (LAS-H) into the mixer (Laedige FKM50D) over about 6-7 minutes to neutralize the reaction. (Spindle rotation speed: 150 rpm (Fr number: 2.24), chopper rotation speed: 2880 rpm). In addition, the temperature of the neutralized / granulated product is controlled by flowing cooling water through the jacket of the mixer (jacket temperature 12 ° C., neutralized / granulated material temperature 56 ° C.) to prepare particles. % Equivalent amount of A-type zeolite was added, stirred for 30 seconds, surface-modified and sprayed with perfume to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 11 (average particle) Diameter 380 μm, bulk density 0.80 g / mL).

Production Method of Surfactant-Containing Particle Group 12 Using a FS-1200 high-speed mixer / granulator manufactured by Fukae Industry Co., Ltd., a high bulk density powder detergent having the composition shown in Table 4 below was prepared in units of 750 kg according to the following operation. .

  Part of zeolite A, sodium carbonate, sodium sulfate, CMC-Na, layered silicate, sodium salt of acrylic acid / maleic acid copolymer, optical brightener, soap with mixer, stirrer speed 100 rpm, shearing machine Dry blended at a speed of 2000 rpm for 60 seconds. Water (equivalent to 0.375%) was added and the mixer was run for 90 seconds at the same stirrer and shear speed. LAS-H was added in 300 seconds while the mixer was operated at a stirrer speed of 80 rpm and a shearer speed of 2000 rpm. The temperature was maintained at 50 ° C. or lower with a cooling jacket through which water passed. When neutralization was completed, water as a binder (equivalent to 1.4%) and a nonionic surfactant were added to the mixer, and granulated for 180 seconds at a stirrer speed of 100 rpm and a shearing machine speed of 2000 rpm. The temperature was maintained at 50 ° C. or lower by a cooling jacket through which water passed. The product obtained in this step was a granular solid.

  The mixer shear was stopped, and while stirring the stirrer at a speed of 90 rpm for 120 seconds, 11% equivalent of A-type zeolite was added to modify the surface, and the perfume was sprayed to obtain surfactant-containing particles.

  In order to color a part of the obtained surfactant-containing particles, a 20% aqueous dispersion of a dye was sprayed in the same manner as in the surfactant-containing particle group 1, and the surfactant-containing particle group 12 (average particle) Diameter 370 μm, bulk density 0.85 g / mL).

The components in Table 3 are shown.
Α-SF-Na: α-sulfo fatty acid alkyl ester (methyl ester (Pastel M-14, Pastel M-16 (manufactured by Lion Oleochemical Co., Ltd.) mixed at 2: 8)) is disclosed in JP 2001-64248 A Sulfonated in accordance with the method disclosed in Example 1 of the Japanese Patent Publication and extracted as an α-sulfo fatty acid alkyl ester after the esterification step and neutralized with sodium carbonate)
LAS-K: linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid (Lypon LH-200 (96% pure LAS-H) manufactured by Lion Co., Ltd.) 48% potassium hydroxide when preparing the surfactant composition Neutralize with aqueous solution). The compounding quantity in Table 12 shows the mass% as LAS-K.
LAS-Na: LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Co., Ltd. neutralized with sodium carbonate)
AOS-K: α-olefin sulfonate potassium having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
AOS-Na: α-olefin sulfonic acid sodium salt having 14 carbon atoms (Liporan PJ-400 manufactured by Lion Corporation)
AS-Na: Sodium lauryl sulfate (Nikko Chemicals SLS) (AS-Na pure content 95.7%)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289)
Nonionic surfactant 1: 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 Nonionic surfactant 2: ECOROL 26 (carbon number of 12 to 16 manufactured by ECOGREEN) Ethylene oxide average 6 mol adduct of alcohol having an alkyl group) PEG 6000: Polyethylene glycol (product name: PEG # 6000M, manufactured by Lion Corporation)
・ Fluorescent brightener A: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)
・ Fluorescent brightener B: Chino Pearl AMS-GX (Ciba Specialty Chemicals Co., Ltd.)
・ No. 1 sodium silicate: JIS No. 1 sodium silicate (manufactured by Nippon Chemical 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.)
-Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.)
-STPP: sodium tripolyphosphate-Zeolite A: A-type zeolite (manufactured by Mizusawa Chemical Co., Ltd.)
・ Zeolite B: P-type zeolite (DOUCIL A24 manufactured by Crossfield)
Layered silicate: crystalline layered sodium silicate (manufactured by Clariant Japan, SKS-6)
・ Polymer A: sodium salt of acrylic acid / maleic acid copolymer, manufactured by BASF, brand name Socaran CP7
-Polymer B: Sodium polyacrylate, manufactured by BASF Corporation, trade name Socaran PA30
HIDS: hydroxyiminodisuccinic acid tetrasodium ASDA: aspartic acid diacetic acid tetrasodium (Mitsubishi Rayon Crewat Bi-ADS / ASDA-4Na)
MGDA: trisodium methylglycine diacetate (Trilon M manufactured by BASF)
Fragrance a: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance b: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance c: Fragrance composition C shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance d: Fragrance composition D shown in JP-A-2002-146399 [Table 11] to [Table 18]
-Dye A: Ultramarine (Daiichi Seika Kogyo, Ultramarine Blue)
-Dye B: Pigment Green 7 (manufactured by Dainichi Seika Kogyo)
・ Sodium carbonate: manufactured by Tokuyama Corporation (trade name: soda ash dense)

The components in Table 4 are shown.
Α-SF-Na: α-sulfo fatty acid alkyl ester (methyl ester (Pastel M-14, Pastel M-16 (manufactured by Lion Oleochemical Co., Ltd.) mixed at 2: 8)) is disclosed in JP 2001-64248 A Sulfonated in accordance with the method disclosed in Example 1 of the Japanese Patent Publication and extracted as an α-sulfo fatty acid alkyl ester after the esterification step and neutralized with sodium carbonate)
LAS-Na: LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Co., Ltd. neutralized with sodium carbonate)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289)
Nonionic surfactant 3: Pastel M-181 (Methyl oleate manufactured by Lion Oleochemical Co., Ltd.) adduct with an average of 15 moles of ethylene oxide Optical brightener A: Tinopearl CBS-X (Ciba Specialty Chemicals Co., Ltd.) ) Made)
・ Fluorescent brightener B: Chino Pearl AMS-GX (Ciba Specialty Chemicals Co., Ltd.)
・ White carbon: Silica fine powder (Tokuyama, Tokuyama Co., Ltd.)
・ Montmorillonite: Montmorillonite (SUD CHEMIE round rosyl powder)
Layered silicate: crystalline layered sodium silicate (manufactured by Clariant Japan, SKS-6)
-Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.)
-STPP: sodium tripolyphosphate-Zeolite A: A-type zeolite (manufactured by Mizusawa Chemical Co., Ltd.)
・ Polymer A: sodium salt of acrylic acid / maleic acid copolymer, manufactured by BASF, brand name Socaran CP7
CMC-Na: carboxymethylcellulose sodium (trade name: Daicel 1130, manufactured by Daicel Chemical Industries)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
Fragrance a: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
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 heating.
・ Sodium carbonate: manufactured by Tokuyama Corporation (trade name: soda ash dense)

[Examples 1 to 6, Comparative Example 1]
In accordance with the composition shown in Table 5, the bleaching compositions of Examples 1 to 6 and Comparative Example 1 were prepared in accordance with the conventional method of powder bleaching composition. Each bleaching composition was evaluated by the following method. The results are also shown in Table 5. In addition, the average particle diameter of the obtained bleaching agent composition was 300-800 micrometers, and the bulk density was 0.7-1.0 g / mL.

[Examples 7 to 16, Comparative Example 2]
According to the composition shown in Table 6, each component was mixed with a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, baffle plate with a clearance of 20 mm from the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7L. 2) and rolled and mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to obtain the bleaching detergent compositions of Examples 7 to 16 and Comparative Example 2. About the bleaching composition obtained by the Example and the comparative example, it evaluated by the following method.

[Evaluation method of bleaching power]
Preparation of curry-stained cloth (1) 5 packs of retort curry (bon curry gold medium hot (Otsuka Foods Co., Ltd., content 200 g / 1 pack)) warmed with hot water for 5 minutes was filtered using a case to obtain a solid The material was removed, and 5 pieces of 25 × 30 cm plain weave cotton cloth (# 100) were immersed in the solution, and uniformly adhered while warming for 30 minutes. The cloth was taken out, rinsed with tap water until the washing solution was no longer colored, dehydrated and air-dried, and then used as a 5 × 5 cm test piece.
Preparation of curry-contaminated cloth (2) 5 packs of retort curry (bon curry gold medium hot (Otsuka Foods Co., Ltd., content 200 g / 1 pack)) warmed with hot water for 5 minutes was filtered using a case and solidified. The thing was removed and the curry liquid was obtained. 0.5 mL of this solution was dropped onto the center of a 5 × 5 cm plain weave cotton cloth (# 100), and then spread with a spatula so that the curry spot had a diameter of about 3 cm. Thereafter, the product naturally dried for 3 hours was used as a contaminated cloth and subjected to an experiment.

Bleaching power-1 (bleaching agent composition)
The powder bleach composition shown in Table 5 was prepared as above by preparing 200 mL of a test solution having a concentration of 0.5% by mass (prepared to 3 ° DH hard water using 25 ° C. deionized water and calcium chloride). 5 sheets of dirty cloth (1) were left for 1 hour. Thereafter, rinsing with tap water was performed for 2 minutes and dehydration was performed for 1 minute, followed by air drying at 25 ° C. for 12 hours.
The raw cloth and the reflectance before and after washing were measured with NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter, the bleaching power was determined by the following formula, and the bleaching performance was evaluated. The bleaching power was determined according to the following evaluation criteria by obtaining an average value of bleaching power for five sheets of contaminated cloth.

<評価基準>
×：基準組成に比べて漂白力が低い
△：基準組成に比べて漂白力が同等以上０％以上＋１０％未満
○：基準組成に比べて漂白力が高く、＋１０％以上１５％未満
◎：基準組成に比べて漂白力が著しく高く、＋１５％以上
基準組成：（２５℃、３°ＤＨ、３０分間つけ置き）
過炭酸ナトリウム５０％、炭酸ナトリウム５０％（漂白力４５％）

<Evaluation criteria>
×: Bleaching power is lower than that of the reference composition Δ: Bleaching power is equal to or higher than 0% and less than + 10% compared to the reference composition ○: Bleaching power is higher than that of the reference composition, and + 10% and lower than 15% ◎: Standard Bleaching power is significantly higher than the composition, + 15% or more Reference composition: (25 ° C., 3 ° DH, left for 30 minutes)
Sodium percarbonate 50%, sodium carbonate 50% (bleaching power 45%)

Bleaching power-2 (Bleaching detergent composition)
U. S. A Terg-O-Tometer from Testing was used, and 5 soiled fabrics (2) obtained above and a knitted fabric were added thereto to adjust the bath ratio to 30 times. After adding 150 mL of water with a predetermined hardness and temperature (prepared to 3 ° DH hard water using 25 ° C. deionized water and calcium chloride), 1.35 g of bleaching detergent composition was added and stirred at 120 rpm for 1 minute And left for 30 minutes. Thereafter, 750 mL of water having a predetermined hardness and temperature (prepared to 3 ° DH hard water using 25 ° C. deionized water and calcium chloride) was added, washed for 10 minutes, rinsed with running water for 1 minute, and dehydrated and dried.
The raw cloth and the reflectance before and after washing were measured with NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter, the bleaching power was determined as described above, and the bleaching performance was evaluated. The bleaching power was evaluated according to the following criteria by obtaining an average value of bleaching power for five sheets of contaminated cloth.

<Evaluation criteria>
×: Bleaching power is lower than that of the reference composition Δ: Bleaching power is equal to or higher than 0% and less than + 10% compared to the reference composition ○: Bleaching power is higher than that of the reference composition, and + 10% and lower than 15% ◎: Standard Bleaching power is significantly higher than the composition, + 15% or more

Standard composition Sodium percarbonate 4%, surfactant-containing particle group 1 94%, enzyme A 2% (bleaching power 35%)

[Clothing damage / coloration evaluation method]
The powder bleaching composition and the bleaching detergent composition shown in Tables 5 and 6 were subjected to damage and coloring tests by the following methods.
A white rayon cloth (6 × 6 cm for JIS dyeing fastness test) is placed on a petri dish (diameter 9 cm, height 1.5 cm), and 2.5 g of the bleaching composition shown in Tables 5 and 6 is placed thereon. Then, a rayon cloth (same as above) was placed on top. Thereafter, 2.5 g of 40 ° C. tap water was gently poured from above and allowed to stand at room temperature for 24 hours, followed by gentle rinsing, observation of cloth damage and coloring, and evaluation according to the following criteria. Only the coloring was evaluated for the bleaching detergent compositions in Table 6.

<Criteria for clothing damage>
1: Cracks and breaks in the cloth 2: Small holes are opened in the cloth 3: The cloth becomes thin and tears when pulled 4: The cloth becomes thin and pulls to open small holes 5: The cloth becomes thin, but pulls Will not tear or puncture 6: No damage to the fabric

<Coloring standards>
1: Remarkably colored 2: Colored
3: Slightly colored
4: Slightly colored
5: No coloring

[Evaluation method for fading]
The powder bleaching composition and the bleaching detergent composition shown in Tables 5 and 6 were subjected to a fading test by the following method.
Place 6 × 6 cm of cotton cloth (# 100) dyed with Reactive Red 21 on a petri dish (diameter 9 cm, height 1.5 cm), and place powder bleach composition and bleach detergent composition 2.5 g on it, Further, the same dyed cloth as above was covered from above. Thereafter, 2.5 g of 40 ° C. tap water was gently applied from above, left for 2 hours, rinsed gently, observed for fading of the cloth, and evaluated according to the following criteria.

<Criteria for fading of clothing>
1: Locally fading 2: Local fading 3: Overall fading 4: Overall fading 5: No fading

[Evaluation method of storage stability]
The storage stability test was conducted by the following method for the powder bleach composition and the bleach detergent composition shown in Tables 5 and 6.
Put powder bleach composition and bleach detergent composition 400g in a container (with refill pouch 3 layer structure from outside polyethylene / polypropylene / nylon = 130μm / 25μm / 15μm, with pinhole of 0.3mm in diameter), 45 ° C After 2 W storage at 25 ° C. recycling conditions (45 ° C./humidity 85% 16 h, 25 ° C./humidity 65% 8 h), the residual rate of sodium percarbonate in the composition was measured by the iodometry method. From this, the residual rate of sodium percarbonate was measured. The following evaluation criteria are used in the table.
Residual rate of sodium percarbonate (%) =
(Concentration of sodium percarbonate after storage) / (initial concentration of sodium percarbonate) × 100

<Evaluation criteria for residual rate of sodium percarbonate>
5 points: over 90%
4 points: over 80% to 90% or less 3 points: over 70% to 80% or less 2 points: over 60% to 80% or less 1 point: over 40% to 60% or less 0 points: 0 to 40% or less

The components in Table 5 are shown.
・ Peroxide-1: Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-Z, effective oxygen content: 10.9%, sodium percarbonate / sodium carbonate / carbonic acid for non-hazardous material Blended with sodium hydride = 77/3/20)
Peroxide-2: coated sodium percarbonate: sodium percarbonate coated with silicic acid and sodium borate (Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-D, effective oxygen amount 13.2%))
・ Peroxide-3: Sodium perborate (trade name: Belbon, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
NRE5: Nonionic surfactant (alkyl chain length 12 to 14, ethylene oxide average addition mole number is 5, ethylene oxide 3 to 7 mol adduct is 90% or more of the whole (pure content: 90%) (Lion Corporation)
NRE9: Nonionic surfactant (alkyl chain length 12-14, ethylene oxide average addition mole number is 9, ethylene oxide 7-11 mol adduct is 90% or more of the whole (pure content: 90%) (Lion Corporation)
-BRE15: Nonionic surfactant (alkyl chain length 12-15, ethylene oxide average added mole number 15 (pure content: 90%) manufactured by Lion Corporation)
LAS-Na: LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Co., Ltd. neutralized with sodium carbonate)
Α-SF-Na: α-sulfo fatty acid alkyl ester (methyl ester (Pastel M-14, Pastel M-16 (manufactured by Lion Oleochemical Co., Ltd.) mixed at 2: 8)) is disclosed in JP 2001-64248 A Sulfonated in accordance with the method disclosed in Example 1 of the Japanese Patent Publication and extracted as an α-sulfo fatty acid alkyl ester after the esterification step and neutralized with sodium carbonate)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289)
HEDP-4Na: 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (manufactured by Solusia Japan Co., Ltd., trade name: Dequest 2016D)
Enzyme 1: manufactured by Novozymes (trade name: Everase 8.0T)
-Bleach activator granulated product 1: 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleach activator, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)] Parts, sodium α-olefin sulfonate powder product having 14 carbon atoms (Lipolane PJ-400 (manufactured by Lion Corporation)) supplied to Hosokawa Micron's Extrude Ohmics EM-6 type so as to have a ratio of 5 parts by mass Then, kneading extrusion (kneading temperature 60 ° C.) was performed to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. This extruded product (cooled to 20 ° C. with cold air) was introduced into Fitzmill DKA-3 type manufactured by Hosokawa Micron Co., Ltd., 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 of about 700 μm bleach activator granulation 1 was obtained. Bleach activator granulation 2: Bleach activator granulation except that sodium 4-dodecanoyloxybenzenesulfonate was used as the bleach activator. In the same manner as in Example 1, a bleaching activator granulated product 2 was prepared.

As a raw material for the synthesis of sodium 4-dodecanoyloxybenzenesulfonate, sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), lauric acid chloride (Tokyo) The synthesis was carried out by the following method using Kasei Kogyo 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%.

・ Sodium carbonate: manufactured by Tokuyama Corporation (trade name: soda ash dense)
Fragrance A: Fragrance composition A shown in Tables 1 to 7 of JP 2003-89800 A
Fragrance B: Fragrance composition B shown in Tables 1 to 7 of JP-A-2003-89800
Fragrance C: Fragrance composition C shown in Tables 1 to 7 of JP-A-2003-89800
・ White carbon: Silica fine powder (Tokuyama, Tokuyama Co., Ltd.)
・ Zeolite A: Type A zeolite (manufactured by Mizusawa Chemical Co., Ltd.)
・ Sodium 4-borate: Sodium tetraborate-pentahydrate (trade name: Neobor, manufactured by Borax)

The components in Table 6 are shown below.
・ Peroxide-1: Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-Z, effective oxygen content: 10.9%, sodium percarbonate / sodium carbonate / carbonic acid for non-hazardous material Blended with sodium hydride = 77/3/20)
Peroxide-2: coated sodium percarbonate: sodium percarbonate coated with silicic acid and sodium borate (Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-D, effective oxygen amount 13.2%))
HEDP-4Na: 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (manufactured by Solusia Japan Co., Ltd., trade name: Dequest 2016D)
Enzyme A: Evalase 8T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Celzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) Enzyme B: Cannase 12T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Celzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) mixture / bleach activator granule 1: 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleaching activator, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion)], α-carbon having 14 carbon atoms Sodium olefin sulfonate powder product (Lipolane PJ-400 (manufactured by Lion Corporation)) 5 parts by mass Supplied to Hosokawa Micron Extrude-O Mix EM-6 type as a diameter to obtain a noodle-shaped extruded product of 0.8mmφ by kneading extruder (kneading temperature 60 ° C.). This extruded product (cooled to 20 ° C. with cold air) was introduced into Fitzmill DKA-3 type manufactured by Hosokawa Micron Co., Ltd., 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 of about A 700 μm bleach activator granulated product 1 was obtained.
Bleach activator granulated product 2: Bleach activator granulated product 2 in the same manner as Bleach activator granulated product 1 except that sodium 4-dodecanoyloxybenzenesulfonate was used as the bleach activator. Was prepared.

As a raw material for the synthesis of sodium 4-dodecanoyloxybenzenesulfonate, sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), lauric acid chloride (Tokyo) The synthesis was carried out by the following method using Kasei Kogyo 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%.

Bleach activator granulated product 3: Bleach activator granulated product 3 in the same manner as Bleach activator 1 granulated product, except that sodium 4-nonanoyloxybenzenesulfonate was used as the bleach activator. Was prepared.

Sodium p-phenolsulfonate (reagent manufactured by Kanto Chemical Co., Inc.), N, N-dimethylformamide (reagent manufactured by Kanto Chemical Co., Ltd.), pelargonic acid chloride (Tokyo) The synthesis was carried out by the following method using Kasei Kogyo Co., Ltd. reagent) and acetone (Kanto Chemical Co., Ltd. reagent). 100 g (0.51 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of N, N-dimethylformamide, and 90 g (0.51 mol) of pelargonic acid chloride was mixed at 50 ° C. with stirring with a magnetic stirrer. It was added dropwise over a period of minutes. Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, purification was performed by recrystallization in a solvent of water / acetone = 1/1 (mol ratio) to obtain 146 g of crystals of sodium nonanoyloxybenzenesulfonate.
-Cellulose powder: Trade name: Arbocel FD600 / 30, manufactured by Rettenmeier-Cationic surfactant: Praepagen HY (C12 / C14-Alkyl dihydroxyethyl methyl ammonium chloride manufactured by Clariant Japan)
Amorphous silicate A: Britesil H24 (manufactured by PQ Corporation)
White carbon: fine silica powder (Tokuyama, Tokuyama Co., Ltd.)

[Examples 17 to 19, Comparative Examples 3 to 4]
According to the composition shown in Table 7, the detergent composition for automatic dishwashers of Examples 17-19 and Comparative Examples 3-4 was prepared according to the conventional method of the detergent composition for automatic dishwashers. The cleaning composition for each automatic dishwasher was evaluated according to the following method. The results are also shown in Table 7.

[Evaluation method of bleaching power]
Preparation of a coffee cup with tea stains In a white coffee cup (inner diameter 70 mm, height 70 mm), pour 200 mL of boiling water for one tea pack of tea (Towering Company Orange Peco) and leave for 5 minutes, then remove the tea pack It was. The tea solution was discharged from the cup, and the test cup was left for 5 days without being rinsed.
Three test cups as described above were loaded into an automatic dishwasher (manufactured by Matsushita Electric Industrial Co., Ltd., NP-50SX3), and standard course washing was performed using 6 g of the cleaning composition for automatic dishwashers shown in Table 7. The finish was evaluated by sensory evaluation based on the following criteria.
<Evaluation criteria for bleaching power>
X: Dirt is not removed at all △: Dirt residue is slightly recognized ○: Dirt residue is not visually recognized, but feels a little uncomfortable when touched ◎: Dirt residue is visually observed And no discomfort such as roughness

[Evaluation method of storage stability]
The bleaching composition shown in Table 7 was subjected to a storage stability test by the following method.
400 g of bleaching composition is put in a container (from outside, refillable pouch three-layer structure polyethylene / polypropylene / nylon = 130 μm / 25 μm / 15 μm, with pinhole of 0.3 mm in diameter), and the recycling conditions at 45 ° C. and 25 ° C. (45 After 2 W storage at 25 ° C./humidity 85% 16 h, 25 ° C./humidity 65% 8 h), the residual rate of sodium percarbonate in the composition was measured by the iodometry method. It was measured. The following evaluation criteria are used in the table.
Residual rate of sodium percarbonate (%) =
(Concentration of sodium percarbonate after storage) / (initial concentration of sodium percarbonate) × 100
<Evaluation criteria for residual rate of sodium percarbonate>
5 points: over 90%
4 points: over 80% to 90% or less 3 points: over 70% to 80% or less 2 points: over 60% to 80% or less 1 point: over 40% to 60% or less 0 points: 0 to 40% or less

[Examples 20 to 23, Comparative Examples 5 to 6]
According to the composition shown in Table 8, Examples 20-23 and Comparative Examples 5-6 washing tub cleaners were prepared. Each washing tub cleaner was evaluated by the following method. The results are also shown in Table 8.

[Evaluation method of cleaning power]
Preparation of Test Piece A plastic plate obtained by cutting a washing machine tub of a fully automatic washing machine to which dirt such as black mold adhered to a 7 × 5 cm was used as a test piece.
Evaluation of Detergency A cleaning solution was prepared by dissolving 5 g of the washing tub cleaner shown in Table 8 in 1 L of tap water at 20 ° C. The test piece described above was immersed in this cleaning solution for 3 hours. Thereafter, 1 L of 20 ° C. tap water was placed in a 1 L beaker, and the test piece after immersion was rinsed by rotating 20 times up and down. Thereafter, the degree of dirt removal (area ratio) was evaluated by comparison with a photograph of a test piece before cleaning.

<Evaluation criteria for the degree of dirt removal>
5: Over 80% to 100% or less 4: Over 60% to 80% or less 3: Over 40% to 60% or less 2: Over 20% to 40% or less 1: 0 to 20% or less

[Evaluation method of storage stability]
About the washing tub cleaner shown in Table 8, the storage stability test was done with the following method.
Put 400g of washing tub cleaner into a container (from outside, refillable pouch 3 layer structure polyethylene / polypropylene / nylon = 130μm / 25μm / 15μm, with pinhole of 0.3mm in diameter) and recycle conditions (45 ℃ ・ 25 ℃) After 2W storage at a humidity of 85% 16h, 25 ° C and humidity 65% 8h), the residual rate of sodium percarbonate in the washing tub cleaner is measured by the iodometry method, and the residual rate of sodium percarbonate is measured from the following formula. did. The following evaluation criteria are used in the table.
Residual rate of sodium percarbonate =
(Concentration of sodium percarbonate after storage) / (initial concentration of sodium percarbonate) × 100

<Evaluation criteria for residual rate of sodium percarbonate>
5 points: over 90% 4 points: over 80% to 90% or less 3 points: over 70% to 80% or less 2 points: over 60% to 80% or less 1 point: over 40% to 60% or less 0 point: 0 ~ 40% or less

The components in Table 7 are shown below.
・ Peroxide-1: Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-Z, effective oxygen content: 10.9%, for non-hazardous substances, sodium percarbonate / sodium carbonate / carbonic acid Blended with sodium hydride = 77/3/20)
Peroxide-2: coated sodium percarbonate: sodium percarbonate coated with silicic acid and sodium borate (Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-D, effective oxygen amount 13.2%)
・ Peroxide-3: Sodium perborate (trade name: Belbon, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
-POE alkyl ether-1: pullulaf LF-403 (manufactured by BASF)
-POE alkyl ether-2: Plurafac LF-1300 (manufactured by BASF)
HEDP-4Na: 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (manufactured by Solusia Japan Co., Ltd., trade name: Dequest 2016D)
Enzyme 1: manufactured by Novozymes (trade name: Everase 8.0T)
Enzyme 4: manufactured by Novozymes (trade name: Duramil 60T)
-Bleach activator granulated product 1: 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleach activator, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)] Parts, sodium α-olefin sulfonate powder product having 14 carbon atoms (Lipolane PJ-400 (manufactured by Lion Corporation)) supplied to Hosokawa Micron's Extrude Ohmics EM-6 type so as to have a ratio of 5 parts by mass Then, kneading extrusion (kneading temperature 60 ° C.) was performed to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. This extruded product (cooled to 20 ° C. with cold air) was introduced into Fitzmill DKA-3 type manufactured by Hosokawa Micron Co., Ltd., 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 of about A 700 μm bleach activator granulated product 1 was obtained. Bleach activator granulated product 4: Tetraacetylethylenediamine granulated product (trade name: TAED4049, manufactured by Clariant Japan Co., Ltd., pure content: 86%).
・ Sodium carbonate: manufactured by Tokuyama Corporation (trade name: soda ash dense)
Layered silicate: crystalline layered sodium silicate (manufactured by Clariant Japan, SKS-6)
Citric acid 3Na: Purified sodium citrate L (manufactured by Fuso Chemical Industry Co., Ltd.)
・ Polymer A: sodium salt of acrylic acid / maleic acid copolymer, manufactured by BASF, brand name Socaran CP7
Silicic anhydride: Britesil H24 (manufactured by PQ Corporation)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
Fragrance A: Fragrance composition A shown in Tables 1 to 7 of JP 2003-89800 A
Fragrance B: Fragrance composition B shown in Tables 1 to 7 of JP-A-2003-89800

The components in Table 8 are shown below.
・ Peroxide-1: Sodium percarbonate: Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-Z, effective oxygen content: 10.9%, for non-hazardous substances, sodium percarbonate / sodium carbonate / carbonic acid Blended with sodium hydride = 77/3/20)
Peroxide-2: coated sodium percarbonate: sodium percarbonate coated with silicic acid and sodium borate (Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-D, effective oxygen amount 13.2%))
・ Peroxide-3: Sodium perborate (trade name: Belbon, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
・ Peroxide-4: 45% potassium persulfate (DuPont)
LAS-Na: LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Corporation) neutralized with sodium carbonate AS-Na: Sodium lauryl sulfate (Nikko Chemicals SLS) (AS-Na pure content 95.7%)
・ Alcohol ethoxylate EO5: Leocol 50, manufactured by Lion Co., Ltd. ・ HEDP-4Na: 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (manufactured by Solusia Japan Co., Ltd., trade name: DAIQuest 2016D)
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
・ White carbon: Silica fine powder (Tokuyama, Tokuyama Co., Ltd.)
-Bleach activator granulated product 1: 70 parts by mass of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals) as a bleach activator, 20 parts by mass of PEG [polyethylene glycol # 6000M (manufactured by Lion Corporation)] Parts, sodium α-olefin sulfonate powder product having 14 carbon atoms (Lipolane PJ-400 (manufactured by Lion Corporation)) supplied to Hosokawa Micron's Extrude Ohmics EM-6 type so as to have a ratio of 5 parts by mass Then, kneading extrusion (kneading temperature 60 ° C.) was performed to obtain a noodle-like extruded product having a diameter of 0.8 mmφ. This extruded product (cooled to 20 ° C. with cold air) was introduced into Fitzmill DKA-3 type manufactured by Hosokawa Micron Co., Ltd., 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 of about A 700 μm bleach activator granulated product 1 was obtained.

Claims (2)

(A) Bleach activation catalyst having a transition metal complex structure 0.1 to 50% by mass
(B) Surfactant 0.1-50 mass%
(C) 10 to 90% by mass of the binder compound
The amount of transition metal that does not form a complex contained in the bleach activated catalyst in the granulated product is 1.0% by mass or less based on the bleach activated catalyst. A bleach-activated catalyst granulated product characterized in that: A bleaching composition comprising the bleach-activated catalyst granule according to claim 1 and a peroxide which dissolves in water and generates hydrogen peroxide.