KR20060063785A - Bleach composition and bleaching detergent composition - Google Patents

Abstract

A bleach composition characterized by comprising (a) a peroxide capable of generating hydrogen peroxide when dissolved in water, (b) a fiber powder insoluble or slightly soluble in water which is selected from among powdered cellulose, silk powder, wool powder, nylon powder, and polyurethane powder, and (c) (c-1) a bleaching activating catalyst and/or (c-2) a bleaching activator; and a bleaching detergent composition comprising (a) a peroxide capable of generating hydrogen peroxide when dissolved in water, (b) a fiber powder insoluble or slightly soluble in water which is selected from among powdered cellulose, silk powder, wool powder, nylon powder, and polyurethane powder, (c) (c-1) a bleaching activating catalyst and/or (c-2) a bleaching activator, and (d) a surfactant.

Description

Bleach composition and bleaching detergent composition

The present invention relates to a bleach composition and a bleaching detergent composition, and more particularly, even when used under severe high concentration conditions when misused, an oxygen-based bleach composition and a bleaching agent having high bleaching power by suppressing damage and discoloration of clothes, etc. A cleaning composition.

Oxygen-based bleaching agents have been the mainstream of clothing bleaching agents because they are characterized by their ability to be used in materials with color patterns. On the other hand, the oxygen-based bleaching agent is inferior to the chlorine-based bleaching agent, so its improvement is required.

In order to improve the bleaching power of oxygen-based bleaching agents, many studies have been conducted on bleaching activators using organic peracids, bleaching activating catalysts containing metal atoms, and the like.

It is well known that bleach activators are converted to organic peracids by reaction with hydrogen peroxide and exhibit high bleaching power against stains and stains.

Meanwhile, a method of using a bleach activating catalyst is disclosed in Nature, Vol. 369 (1994) pages 637-639, J. Am. Chem. Soc., Vol. 115 (1993), pages 1772-1773, discloses a mechanism in which a complex in a bleach solution catalytically activates hydrogen peroxide to impart a high bleaching effect on stains and stains. Therefore, high bleaching power can be obtained efficiently even with a small amount of complexes.

However, these techniques can achieve high bleaching power, but if the clothing is repeatedly washed or the composition is directly in contact with the clothes at a high concentration, the clothes become thinner, causing problems such as puncture and fading of the colored clothes. Known.

Such damage and discoloration of clothing seems to be caused by oxygen-activated species produced by abnormal decomposition of hydrogen peroxide.

Such clothes may be damaged or discolored when a powder or bleaching agent is not sufficiently dissolved in the dip-bleaching process by using a tub or a washing tank. It is noticeable when it comes in contact with clothing.

In order to suppress the damage and discoloration of clothes by the bleach activator and the bleach activating catalyst, a suppression technique by intimately mixing the bleach activator with mineral substances such as acid clay and bentonite is disclosed in Japanese Patent Application Laid-Open No. 6 Disclosed in Japanese Patent Application Laid-Open No. 9-511774, disclosed in -057297, wherein a suppression technique by combining a catalyst with a radical trapping agent such as dibutylhydroxytoluene and mono-t-butylhydroquinone is disclosed. The suppression technique by combining the catalyst with the crystalline layered silicate is disclosed in Japanese Patent Laid-Open No. 9-137196, and the suppression technique by combining the catalyst with the clay mineral is disclosed in Japanese Patent Laid-Open No. 9-137196. -025499.

However, these techniques are insufficient to efficiently suppress damage to clothes and the like while exhibiting high bleaching power and preventing coloring. That is, the suppression technique using a radical trapping agent is a technique which inactivates the generated oxygen active species and suppresses damage and discoloration. On the other hand, there is a drawback that the radical trapping agent reacted with the oxygen active species stains and stains the garment. On the other hand, by granulating with a bleach activator or a bleach activating catalyst by using a water-insoluble substance such as a mineral substance, crystalline layered silicate, clay mineral, etc. to maintain the distance from the garment and physically reduce the contact opportunity. It may be difficult to dissolve so that the solubility may not be sufficiently secured so that a sufficient bleaching effect may not be exerted. In addition, the bleach activator and the bleach activating catalyst gradually dissolved while being in contact with the clothes for a long time without being sufficiently dissolved, resulting in high concentration near the clothes, resulting in damage or fading, which was also insufficient as an inhibitory effect.

On the other hand, Japanese Unexamined Patent Publication No. 2003-64574 proposes a detergent composition containing water-insoluble solid particles to prevent deterioration of fabrics, and discloses international patent applications 2002-502456 and Japanese Unexamined Patent Publication No. 2000- In 192098, a detergent containing cellulose as a disintegrant has been proposed.

However, there has been a demand for bleaches and bleach cleaners which have high bleaching power and which also inhibit damage to clothes, discoloration and fading of dyes.

Disclosure of the Invention

An object of the present invention is to provide an oxygen-based bleach composition and a bleaching detergent composition having high bleaching power by suppressing damage and discoloration of clothing and the like even under severe conditions at the time of misuse and preventing coloring.

By adding a specific water-insoluble or poorly water-soluble fiber powder to the bleach composition and the bleach cleaner composition, the present inventors suppress damage or discoloration of clothing and the like even under severe conditions at the time of misuse, and do not cause coloration, thereby providing high bleaching power. It was found possible to have.

That is, the present inventors have a different effect that a specific water-insoluble or poorly water-soluble fiber powder maintains the physical distance between the bleach activator or the bleach activating catalyst and the clothes to inactivate the oxygen active species which causes the damage or discoloration of the clothes. By confirming that damage and discoloration of clothing can be suppressed efficiently, it came to complete this invention.

Accordingly, the present invention provides the following bleach composition and bleach detergent composition.

1. a water-insoluble or poorly water-soluble fiber powder selected from the group consisting of (a) peroxides dissolved in water to generate hydrogen peroxide, (b) powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, and (c) a bleach composition comprising (c-1) a bleach activating catalyst and / or (c-2) a bleach activating agent.

2. (a) peroxides dissolved in water to generate hydrogen peroxide, (b) water insoluble or poorly soluble fiber powders selected from the group consisting of powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, and (c) A bleaching detergent composition comprising (c-1) a bleaching activating catalyst or (c-1) a bleaching activating catalyst, (c-2) a bleaching activator, and (d) a surfactant.

3. Content of (d) component is 10-50 weight%, Bleaching detergent composition of 2 characterized by the above-mentioned.

4. The composition according to any one of 1 to 3, wherein the component (a) is sodium percarbonate.

5. The composition according to 4, wherein the component (a) is coated sodium percarbonate.

6. (b) Component is powdered cellulose, The composition in any one of 1-5 characterized by the above-mentioned.

7. The composition according to any one of 1 to 6, wherein the component (c-1) is contained and the bleaching activation catalyst of the component (c-1) contains manganese.

8. The composition according to 7, wherein the bleaching activating catalyst of component (c-1) is (tris (salicylideneiminoethyl) amine) -manganese complex.

9. (c-1) The composition in any one of 1-8 characterized by containing 0.001-1 weight% of components in a composition.

10. Component (c-2), wherein the bleaching activator of component (c-2) is 4-decanoyloxybenzoic acid or 4-nonanoyloxybenzenesulfonate sodium, characterized in that any one of 1 to 9 Described composition.

11.Contains (c-1) and (c-2), the bleaching activation catalyst of component (c-1) is (tris (salicylideneiminoethyl) amine) -manganese complex, (c-2 The bleaching activator of a) component is 4-decanoyloxybenzoic acid or 4-nonanoyloxybenzenesulfonate sodium, The composition according to any one of 1 to 9,

12. The composition as described in any one of 1-11 which contains the granules or molded object containing (b) component and (c) component.

13. A composition according to 12, which contains a binder compound in granules or shaped articles.

14. The composition according to 13, wherein the binder compound is polyethylene glycol having an average molecular weight of 2600 to 9300.

15. The composition according to any one of 12 to 14, further comprising a surfactant in the granules or the molded product.

16. The composition according to any one of 12 to 15, wherein the content of the component (b) is 3 to 50% by weight in the granule or the molded product.

17. The bleach composition according to any one of 12 to 16, wherein the content of the component (b) is 0.05 to 3% by weight in the composition.

18. The bleaching detergent composition according to any one of 12 to 16, wherein the content of the component (b) is 0.005 to 1% by weight in the composition.

Hereinafter, the present invention will be described in more detail. The bleach composition of the present invention is a water-insoluble or poorly water-soluble fiber powder selected from the group consisting of (a) peroxide dissolved in water to generate hydrogen peroxide, (b) powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, And (c) (c-1) a bleaching activating catalyst and / or (c-2) a bleaching activator, wherein the bleaching detergent composition of the present invention comprises (a) a peroxide that is dissolved in water to generate hydrogen peroxide, (b) Water-insoluble or poorly water-soluble fiber powder selected from the group consisting of powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, and (c) (c-1) bleaching activation catalyst or (c-1) bleaching activation catalyst (c-2) a bleach activator and (d) a surfactant. These compositions are prepared as bleach compositions and bleach cleaner compositions in solid form, such as powders, granules, tablets, briquets, sheets or bars.

Here, the bleach composition refers to clothing with detergent at the time of washing, usually by immersing in a tub or a washing tank for 15 minutes to 2 hours in order to remove stains or stains of food on the clothing, and yellow contamination of the clothing after long-term wearing. It is usually used for washing for 5 to 15 minutes in a washing machine in order to remove sebum or black pollution, weak stains or contamination of foods attached to clothes, and to prevent yellow pollution of clothes.

The difference between the bleach composition and the bleach cleaner composition is that the bleaching composition is considered to be important, and that the bleaching power is inferior to the bleaching composition, but the bleaching detergent composition is important. Therefore, the difference in composition is that the amount of the bleach component (peroxide, bleach activating catalyst and / or bleach activator) is higher in the bleach composition, and in terms of the amount of the surfactant, the bleach detergent composition is increased.

Component (a) of the present invention is a peroxide that is dissolved in water to generate hydrogen peroxide. Specific examples of the component (a) include sodium peroxide, sodium perborate, sodium perborate trihydrate, and the like. It is preferable to use sodium peroxide in view of solubility in use and stability in storage. Sodium peroxide is also more preferably coated sodium peroxide in order to improve stability upon storage. In particular, it is preferable to coat with silicic acid and / or silicic acid and boric acid and / or borate. Specifically, as described in Japanese Patent No. 2918991 or the like, sprayed and coated with an aqueous solution of silicic acid and / or an alkali metal silicate solution and boric acid and / or an alkali metal salt solution of boric acid, or a water-insoluble organic compound such as paraffin or wax. In order to use a coated thing or to make it into a non-hazardous thing, it is preferable to use it by powder-blending with various inorganic substances, such as sodium carbonate and sodium hydrogencarbonate. In addition, in the case of a watery composition in the composition, in particular, a bleaching detergent composition, for example, by blending a surfactant, it is preferable to use a coated peroxide coated with sodium percarbonate with silicate and sodium borate. These peroxides can be used 1 type or in combination of 2 or more types as appropriate. The production of coated sodium percarbonate is disclosed in Japanese Unexamined Patent Publications No. 59-196399, USP4526698 (both coated with sodium percarbonate with borate), and Japanese Unexamined Patent Publications No. 4-31498, Japanese Unexamined Patent Publication No. Hei 6-40709. And the method disclosed in Japanese Patent Application Laid-open No. Hei 7-118003. The average particle diameter of the inorganic peroxide is preferably 200 to 1000 µm, more preferably 300 to 800 µm, and in order to satisfy both solubility and stability, particles having a particle diameter of less than 125 µm and particles exceeding 1000 µm include (a) component. It is preferable that it is 10 weight% or less in water. Here, an average particle diameter can be confirmed by methods, such as calculating | requiring a particle size distribution using the sieve mentioned later and calculating from the particle size distribution. In addition, considering the stability of the peroxide, the water content in the bleach composition is preferably 2% by weight or less.

In the present invention, the content of the component (a) is not particularly limited, but in the case of the bleach composition, 20 to 90% by weight is preferable in the composition, more preferably 25 to 90% by weight, more preferably 30 to 90% by weight. . Even if the above range is exceeded, the bleaching effect does not increase with respect to stains or stains on clothing, and yellow contamination of clothes generated after long time wearing, and below the above range, sufficient bleaching effect against stains or stains cannot be obtained. In the case of the bleaching detergent composition, 1 wt% or more and less than 20 wt% is preferable in the composition, more preferably 2 wt% or more and less than 20 wt%. If it is more than the above range, the bleaching effect against slight stains or stains or the yellow stain prevention effect of clothing may not be increased any more, and sufficient surfactant content may not be secured and sufficient washing effects may not be obtained. In addition, less than the above range may not be sufficient as a bleaching detergent composition.

Component (b) of the present invention is a water-insoluble or poorly water-soluble fiber powder selected from powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder. The component (b) mainly acts as an inhibitor of clothing damage or fading. In addition, the water-insoluble or poorly water-soluble fiber powder is a fiber powder having a solubility of less than 0.1 g in 100 g of 25 ℃ deionized water, using the fiber as it is, or frozen or dispersed in a solvent to grind, crushed It is.

Here, powdered cellulose is lumber such as saline or hardwood, hemp or leafwood such as Edgworthia, Japanese mulberry, Diplomorpha, straw, bagasse and bamboo, stem fiber, bark fiber, cotton , Seed plant fibers such as cotton plants and kapok, etc. may be purified or partially hydrolyzed as necessary, and processed fibers such as cotton, hemp, rayon, and the like may be used. will be. Therefore, the microcrystalline cellulose which removed the amorphous part by powdering only hydrolysis, without carrying out grinding | pulverization process, such as Avicel and Celvia by Asahi Kasei Corporation, is not included in the component (b) of this invention, The comparative example mentioned later As shown in Fig. 2, the effect of suppressing damage and fading of clothing and the like is insufficient. The mechanism of this phenomenon is not clear, but it is presumed that the amorphous part has a stronger interaction with the peroxide than the crystalline part. In addition, carboxymethyl cellulose sodium (CMC) or hydroxyethyl cellulose (HEC), which chemically modifies functional groups in various functional groups such as carboxymethyl group and hydroxyethyl group, to increase water solubility, crosslinked carboxymethyl cellulose sodium Cellulose derivatives such as (Ac-Di-Sol) are not included in component (b) of the present invention even if they are water-insoluble or water-soluble, and the effects of the present invention cannot be obtained. That is, the powdered cellulose used in the present invention does not include the microcrystalline cellulose or the cellulose derivative described on page D-1083 of the 7th edition of the Food Additives Process Manual (Hirokawa Shoten, 1999).

Among the above, powdered cellulose, silk powder and wool powder of natural fibers are preferred, powdered cellulose and silk powder are more preferred, and powdered cellulose is particularly preferred.

Specific examples of water-insoluble or poorly water-soluble fiber powders suitable in the present invention include KC FLOC W-400G (manufactured by Nippon Paper Group Inc.), Arbocel BE-600 / 10, Arbocel HB120, Arbocel BE-600 / 30, Arbocel FD 600 / 30, Arbocel TF30HG, Arbocel BWW-40, Arbocel BC-200, Arbocel BE-600 / 20 (manufactured by Retenmeier), Idemit silk powder (manufactured by Idemitsu Phytochemical Co., Ltd.), silk powder (Daito Kasei Kogyo Co., Ltd.) Commercial Limited), 2002 EXDNATCOS Type-S (made by Elf Atochem Ltd.), etc. are mentioned.

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 average fiber length is preferably 150 μm or less, and more preferably 100 μm or less. In consideration of powdering at the time of manufacture, 5 micrometers or more are preferable and especially 10 micrometers or more are preferable. Here, in the present invention, the method for measuring the average particle diameter and the average fiber length is not particularly limited. For example, the particle size may be measured using a particle size distribution measuring device of a laser light scattering method or by a sieve according to the particle size test described in the Japanese Pharmacopoeia. It can confirm by calculating from a distribution, measuring by an electron microscope method, etc. In addition, the fiber powder of the size may be selected from the commercially available materials in the above range, or may be ground or sieved to the size. In this invention, it calculates from the particle size distribution by the sieve based on the test of the particle size described in the Japanese Pharmacopoeia.

As the component (b) of the present invention, the water-insoluble or poorly water-soluble fiber powder may be used as one kind, or a plurality of water-insoluble or poorly water-soluble fiber powders may be mixed and used at an arbitrary ratio.

In the present invention, when the component (b) is not granulated or molded together with the component (c) described later, the content of the composition of the component (b) is preferably 5 to 40% by weight, preferably 10 to 20% by weight in the bleach composition. % Is more preferable. In addition, in the bleach detergent water, 1 to 10% by weight is preferable, and 3 to 10% by weight is more preferable. Even if it is out of the above range, there may be a case where the effect of inhibiting damage or fading of the garment does not increase, and at the same time, in the bleaching detergent composition, a sufficient amount of surfactant may not be secured if it is out of the above range, so that a sufficient cleaning effect may not be obtained. In addition, below the said range, the effect of suppressing damage or fading of clothing may not be sufficient.

In the present invention, when the component (b) is a granule or a molded product together with the component (c) described later, the content of the composition of the component (b) is preferably 0.05 to 3% by weight, and 0.1 to 1% by weight in the bleach composition. % Is more preferable. Moreover, in a bleaching detergent composition, 0.005-1 weight% is preferable and 0.01-0.5 weight% is more preferable.

Thus, the (b) component and (c) component are made into granules or molded products which exist in the vicinity, and the damage and discoloration of clothing by the (c) component are suppressed efficiently by a comparatively small amount of (b) component. It is more preferable because it can be done.

In the case of the bleach composition, the component (c) of the present invention can be used as the (c-1) bleaching activating catalyst to effectively prevent damage or discoloration of clothing caused by the component (c) by a relatively small amount of the component (b). It is more preferable because it can.

While the bleaching activation catalyst (c-1) included in the bleach composition and the bleaching detergent composition acts catalytically in the bleach solution and continues to express the bleaching effect as long as the peroxide is present, a small amount of high bleaching effect can be obtained. It may cause damage or discoloration of clothing. (c-1) Bleaching activating catalysts include transition metal atoms and ligands such as copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum through nitrogen or oxygen atoms. Cobalt, manganese, etc. are preferable as a transition metal to form a complex, and manganese is especially preferable. In this case, any counterion exists that is in equilibrium with the charge generated stoichiometrically by the combination of a transition metal atom and a ligand. In that case, preferred counterions are chloride ions and ammonium ions.

As a preferable ligand in this invention, Unexamined-Japanese-Patent No. 2000-144188, Unexamined-Japanese-Patent No. 2000-54256, Unexamined-Japanese-Patent No. 2000-34497, International patent application 2000-508011 and 2000-500518 Japanese Patent Laid-Open No. 11-57488, Japanese Patent Laid-Open No. 11-106790, Japanese Patent Laid-Open No. 11-171893, Japanese Patent Laid-Open No. 11-342341, International Patent Application No. 11 published in Japan -507689, Japanese Patent Application Laid-Open Nos. 11-515049 and 11-507923, Japanese Patent Laid-Open Nos. 9-194886, Japanese Patent Laid-Open No. 8-231987, Japanese Patent Laid-Open No. 8-067687, and International Publications in Japan Patent Application Hei 8-503247, Japanese Patent Application Laid-Open No. 7-065074, Japanese Patent Application Laid-Open No. 7-068558, Japanese Patent Application Laid-Open No. 5-17485, International Publication 94/11479 pamphlet, International Publication 93/15175 Pamphlet, International Patent Applications 2002-530481, 2002-538268 and 2000-515194, published in Japan Ligands disclosed in Japanese Patent Application Laid-Open No. 2002-294290, and the like, and more specific ligands include carboxylate-containing amines, 1,4,7-trimethyl-1,4,7-triazacyclononane and compounds similar thereto, Water-soluble or water-dispersible derivatives, 2,2'-dipyridyl derivatives, 1,10-phenanthroline derivatives, amines, tris (salicylideneiminoethyl) amines with pin and porphyrins, phthalocyanines and their backbones , N, N'-ethylenebis (4-hydroxysalicylideneiminate), 13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3, 3,9, 9-tetramethyl-1H-1,4,8,11-benzotetraazacyclotridecine, 5,12-dimethyl-1,5, 8,12-tetraaza-bicyclo [6,6,2] hexadecane And 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6,6,2] hexadecane. Specific bleach activating catalysts include carboxylate-containing cobalt amine, tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphate, Manganese complexes of porphine or porphyrin derivatives, manganese complexes of phthalocyanine or phthalocyanine derivatives, manganese complexes of 2,2'-dipyridyl derivatives, manganese complexes of 1,10-phenanthroline derivatives, cobalt amines, (tris (salicylic Manganese complex of deniminoethyl) amine), manganese complex of (N, N'-ethylenebis (4-hydroxysalicylideneiminate)), 5,12-dimethyl-1,5,8,12-tetra Aza-bicyclo [6,6,2] hexadecane: manganese (II) chloride, [13,14-dichloro-6,6-diethyl-3,4,8,9-tetrahydro-3,3,9 , 9-tetramethyl-1H-1,4,8,11-benzotetraazacyclotridecine] -iron complex and the like. In the present invention, more preferred bleaching activation catalyst is tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphate, (tris Manganese complex of (salicylideneiminoethyl) amine) and manganese complex of (N, N'-ethylenebis (4-hydroxysalicylideneiminate)), in terms of bleaching power and damage or fading of clothes. Manganese complexes of (tris (salicylideneiminoethyl) amine) are preferred.

The molar ratio of the preferred transition metal atom and ligand of the (b-1) bleaching activation catalyst in the present invention is 1: 1 to 1: 4. If the ratio of the ligand is less than the above ratio, hydrogen peroxide may be decomposed by transition metal atoms which do not form a complex, which may cause a decrease in the bleaching effect. On the other hand, even if the ratio of the ligand is larger than the above ratio, the bleaching effect may not be increased any more, which may result in uneconomic.

In the present invention, when the component (c-1) is not granulated or molded together with the component (b) described above, the preferred content of the component (c-1) in the bleach composition and the bleaching detergent composition is 0.001 to 1 It is weight%, 0.01-0.5 weight% is more preferable in a bleach composition, and 0.005-0.3 weight% is more preferable in a bleaching detergent composition. Even if it exceeds the said range, a bleaching effect may not increase any more, and at the same time, it may become difficult to suppress damage to a garment and fading. Moreover, below the said range, sufficient bleaching effect may not be acquired.

In the present invention, when the component (c-1) is granulated or molded together with the component (b) described above, the preferred content of the component (c-1) in the bleach composition and the bleaching detergent composition is 0.001 to 1% by weight. In a bleaching composition, 0.1-1 weight% is more preferable, and in a bleaching detergent composition, 0.01-0.5 weight% is more preferable.

As described above, in the case of granules or molded products in which the component (b) and the component (c-1) are present in the vicinity, the component (c-1) can be blended in a large amount and the bleaching power can be increased. The component (b) is more preferable because the damage or discoloration of the garment by the component (c-1) can be suppressed efficiently.

The bleach activator (c-2) used in the bleach composition of the present invention is an organic peracid precursor, and is a compound that generates organic peracid by peroxides such as hydrogen peroxide. In order to express the stoichiometric bleaching effect, it is necessary to formulate a high concentration, unlike catalytically acting as (c-1) a bleach activating catalyst. In that case, no damage to the garment such as the bleaching activating catalyst (c-1) occurs, but only the fading of the garment occurs. Specific examples of the bleach activator include tetraacetylethylenediamine, pentaacetylglucose, octanoyloxybenzenesulfonate sodium, nonanoyloxybenzenesulfonate sodium, decanoyloxybenzenesulfonate sodium, undecanoyloxybenzenesulfonate sodium and dodecanoyloxy Sodium benzenesulfonate, undecanoyloxybenzenesulfonate sodium, decanoyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxy Benzene, nonanoyloxybenzene, decanoyloxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene, and the like.

Mention may also be made of the compounds represented by the following formulas (1) and (2):

In the food,

R ¹ is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4, particularly preferably 1 to 3 carbon atoms, which may be divided into an ester group, an amide group or an ether group, and R ⁶ is divided into an ester group, an amide group or an ether group. It is a C1-C8, preferably 2-6 alkylene group which may be sufficient and may be substituted by the hydroxy group. R ² , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group or a hydroxyethyl group. X <^-> is an anion, Preferably it is a halogen ion, a sulfate ion, a fatty acid ion, or a C1-C3 alkyl sulfate ion.

In addition, organic peracids produced from bleach activators exhibit bactericidal activity in the laundry system and also reduce the number of microorganisms remaining in the garments (Yoshitaka Miyama, Satoshi Matsunaga, Seichi Tobe, Kenji Takahashi, Haruo Yoshimura, Teruhisa Satsuki, The 28 ^th Symposium Summary Related to Cleaning, pages 157-165 (1996)). From the viewpoint of bactericidal power, a bleach activator which produces organic peracids of C8 to C12 is particularly preferable. Specific examples of these bleach activators include decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, and the like. Among them, 4-decanoyloxybenzoic acid and 4-fur from the viewpoint of the bleaching effect. Sodium nanoyloxybenzene sulfonate is more preferable. From the viewpoint of the fading inhibitory effect, 4-decanoyloxybenzoic acid and 4-dodecanoyloxybenzenesulfonate sodium are preferable.

In the present invention, the bleaching activator (c-2) is preferably blended as granules or moldings in view of storage stability during storage. The content of the (c-2) bleaching activator in the granules or the molded product when the granules or the molded product does not contain the component (b) or the component (c-1) is preferably 30 to 95% by weight, more preferably. Is 50 to 90% by weight. When content is out of this range, the granulated effect may become difficult to fully be obtained.

It is preferable to make these into granules or molded articles using a binder compound selected from polyethylene glycol, a saturated fatty acid having 12 to 20 carbon atoms, polyacrylic acid having a weight average molecular weight of 1000 to 1000000, or a salt thereof. As polyethyleneglycol, Preferably it is polyethyleneglycol 1000-20000 (average molecular weight 500-25000), More preferably, it is average molecular weight 2600-9300, Especially preferably, it is average molecular weight 7300-9300. The saturated fatty acid having 12 to 20 carbon atoms is preferably a saturated fatty acid having 14 to 20 carbon atoms, more preferably 14 to 18 carbon atoms. In addition, the average molecular weight of polyethyleneglycol in this invention shows the average molecular weight described in cosmetic raw material standard (note 2nd edition). In addition, the weight average molecular weight of polyacrylic acid and its salt is a measured value by the gel permeation chromatography which makes polyethyleneglycol the reference material. Such binder material is used in the granules in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight.

The granules also contain polyoxyalkylene alkyl ethers, olefin sulfonates, alkylbenzene sulfonates, salts of alkyl sulfonic acid esters, or salts of polyoxyethylene alkyl ether sulfonic acid esters to improve the solubility of the bleach activator in the wash bath. Or it is good to use together with surfactant, such as a mixture thereof, The content in granules becomes like this. Preferably it is 0-50 weight%, More preferably, it is 3-40 weight%, Especially preferably, it is 5-30 weight%. As the polyoxyalkylene alkyl ether, the carbon number of the alkyl group is preferably 10 to 15, preferably an addition product of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO). The average added mole number is preferably 4 to 30, more preferably 5 to 15, and the molar ratio of EO / PO is preferably 5/0 to 1 /. 5, More preferably, it is 5/0-1/2. The salt of olefinsulfonic acid is preferably the sodium or potassium salt of α-olefinsulfonic acid having 14 to 18 carbon atoms in the alkyl group. As the salt of the alkylbenzenesulfonic acid, sodium or potassium salts of linear alkylbenzenesulfonic acids having 10 to 14 carbon atoms in the alkyl group are preferable. As the salt of the alkyl sulfate ester, an alkyl group has 10 to 18 carbon atoms, more preferably an alkali metal salt such as sodium salt, and sodium lauryl sulfate ester or myristyl sulfate sodium is particularly preferable. Moreover, as polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-18 alkyl group is preferable, and sodium salt is preferable. Herein, 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, particularly polyoxyethylene lauryl ether sulfate ester sodium (POE = 2 to 5), Polyoxyethylene myristyl ether sodium sulfate (POE = 2-5) is preferred.

In the present invention, granules of bleach activators can be prepared by any method. Moreover, a preferable result can be obtained by melt | dissolving before binder material is added. The binder material is melted and added at 40 to 100 ° C, preferably 50 to 100 ° C, more preferably 50 to 90 ° C. These are stirred and mixed until uniform and then formulated by a conventional granulator. Extrusion granulation is mentioned as a preferable granulation method, It is preferable to set it as the granule of 500-5000 micrometers, Preferably it is 500-3000 micrometers. Moreover, as another granulation method, what makes it into tablet form with a briquette group is mentioned as a preferable granulation method.

Here, it is known that the bleach activator causes hydrolysis due to the presence of an alkaline component and water in the bleach or bleach cleaner during storage, thereby losing the bleaching and bactericidal effect. Therefore, in the present invention, in order to prevent such decomposition, the bleach activator is preferably mixed with a film-forming polymer, zeolite, or the like in addition to the binder or the surfactant and blended into granules.

 The bleach activator of the present invention can also be used as a bleach activating catalyst and granules or moldings in the bleach composition and the bleach detergent composition.

In the present invention, when the component (c-2) is not granulated or molded together with the component (b) described above, the content of the component (c-2) in the bleach composition is preferably 0.1 to 5% by weight. More preferably, the content of (c-2) component in 0.1 to 3% by weight and the bleaching detergent composition is preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight. Even if it exceeds the said range, the bleaching effect may not increase any more, and at the same time, it may become difficult to suppress the fading of clothing. In addition, below the said range, sufficient bleaching effect may not be acquired.

 In the present invention, when the component (c-2) is a granule or a molded product together with the component (b) described above, the content of the component (c-2) in the bleach composition is 0.1 to 10% by weight, more preferably. Preferably 0.2 to 5% by weight. The content of the component (c-2) in the bleaching detergent composition is preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight.

Therefore, the component (c-2) may be incorporated in a large amount, and in the case of granules or moldings in which the components (b) and (c-2) are present in close contact, the bleaching force may be improved, and (c) -2) fading of clothing by the component can be effectively suppressed even by a relatively small amount of the component (b); Therefore, more preferable.

It is also effective to improve the inhibition of damage and discoloration of clothing by the component (c) and the inhibition of degradation of the peroxide when stored so that the components (b) and (c) are as closely present as possible. As a method, a method of forming granules or moldings containing component (b) and (c), or granules or moldings containing component (c) are prepared in advance, and then these are prepared by (b) component or (b) The method of coating with the component which consists of a component and a suitable adduct is mentioned. Among these methods, granules or moldings containing component (b) and component (c) and a binder are preferred in view of ease of manufacture and production cost. Particular preference is given to using granules or moldings containing both the binder compound and the surfactant in order to improve the solubility of the binder compound and component (c) in addition to ease of manufacture and production costs.

In addition, the component (c) may be dissolved and dispersed in a solvent or the like and then dipped or sprayed into the component (b) for granulation so as to improve the solubility of the component (c) and to efficiently exert high bleaching power.

Examples of binder compounds used in granules or moldings include polyethylene glycol 1000 to 20000 (average molecular weight 500 to 25000), saturated fatty acids having 12 to 20 carbon atoms and polyacrylic acid having a weight average molecular weight of 1000 to 1000000 and salts thereof. Can be. More preferred are polyethylene glycol 4000 (average molecular weights 2600 to 3800) to 6000 (average molecular weights 7300 to 9300), in particular polyethylene glycol 6000 (average molecular weights 7300 to 9300), having a melting point of 50 to 65 ° C.

As an example of surfactant used for granules or moldings, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. These can be used combining 1 or 2 or more suitably. Particularly preferred surfactants are polyoxyethylene alkyl ethers having 12 to 15 carbon atoms and 5 to 25 average added moles of ethylene oxide, alkyl sulfates or alkenyl sulfates having 10 to 20 carbon atoms, sodium α-olefinsulfonate having 14 carbon atoms And adducts of ethylene oxide and fatty acid methyl esters having 12 to 16 carbon atoms and an average added mole number of ethylene oxide, fatty acid alkanol amides having 12 to 18 carbon atoms, and amine oxides.

When preparing granules or moldings, as a combination of a binder compound and a surfactant, a combination of sodium C14 -olefin sulfonate and polyethylene glycol 6000 or a combination of sodium lauryl sulfate and polyethylene glycol 6000 is easy to manufacture and produce. In addition to cost, it is preferable from the viewpoint of improving the solubility of the binder compound and the component (c).

In order to improve productivity, it is preferable to add inorganic substances such as sodium sulfate and sodium tetraborate, and organic acid salts such as sodium citrate to the granules or moldings.

The method for producing granules is not particularly limited, but examples of granulation methods include (b) component, (c) component and, if necessary, surfactant and the like in a noodle shape of about 1 mm in diameter using a kneader and an extruder together with a binder compound. Extrusion-molding followed by granulation / powdering using a granulator; dissolving and dispersing component (b), component (c) and, if necessary, a surfactant in a molten binder mixture and then cooling and solidifying the mixture in a mixer to produce a bulky product and then granulating the granules prepared. / Producing by powdering.

In addition, the method of mixing the (b) component, (c) component and surfactant using a stirring granulator, a container rotary granulator or a layered granulator, and granulating by adding a binder mixture while fluidizing the mixture. Can be mentioned.

The particle diameter of the granules is not particularly limited, but in view of solubility and stability, the average particle diameter is 200 to 1200 µm, preferably 300 to 1000 µm. If it is less than the above range, the storage stability of the peroxide may be deteriorated, and if it exceeds the above range, the solubility is poor and a suitable effect may not be obtained. Here, an average particle diameter can be confirmed by the particle size distribution measuring method by calculating from a particle size distribution using the sieve mentioned later.

In the method for producing a molded article, for example, a component (b), a component (c), a binder compound, a surfactant or the like may be mixed with a mixer or kneader as necessary and kneaded, and then kneaded, followed by a porous die or screen using an extrusion molding machine. Extruded through, cut | disconnected, and the method of forming a pellet shaped product is mentioned.

Furthermore, after (b) component, (c) component, binder compound, surfactant, etc. are mixed as needed, it is compression-molded by a tableting machine or a briquetting machine, and it is grind | pulverized with a grinder as needed and adjusts size The method can also be used. In addition, when the bleach composition or the bleaching detergent composition is in tablet form, a mixture of the component (b), the component (c), the binder compound, and a surfactant, if necessary, is prepared in advance, and the mixture is prepared according to the method for producing a multilayer tablet. And the remaining components in the bleach composition or the bleach cleaner composition may be supplied to a tableting machine (mortar) and compression molded to prepare a bleach composition or a bleach cleaner composition.

In the present invention, when the component (b) is a granule or a molded product together with the component (c), the content of the component (b) is preferably 3 to 50% by weight in the granule or the molded product. Moreover, in the case of the bleach composition and the bleaching detergent composition containing the granules or molding containing (b) component, (c) component, and a binder compound, each of (b) component / (c) component / binder compound in a granule or molding The content of is preferably from 3 to 50 wt% / 3 to 90 wt% / 5 to 94 wt%, more preferably from 5 to 30 wt% / 5 to 70 wt% / 10 to 90 wt%. The component (b) is preferably in the above range from the viewpoint of damage or fading to the garment, and the component (c) is preferably in the above range from the viewpoint of the bleaching effect and the damage or fading to the garment, and the binder compound is productive or shaped. The said range is preferable from a viewpoint of fats and oils and solubility.

Moreover, it is preferable to contain surfactant in a granule or molded object in order to dissolve component (c) and a binder compound quickly. The content of the surfactant contained in the granules or the molded product is preferably 1 to 20% by weight, more preferably 1 to 10% by weight. Even if it exceeds the said range, solubility may not improve any more, and below the said range, solubility may be inadequate and may adversely affect the bleaching effect. In the case where the granules contain a surfactant, the surfactant content may be adjusted by reducing the content of the surfactant from the content of the binder compound.

In addition, for the purpose of enhancing the effect of preventing damage to the clothes and fading, it is preferable to contain at least 1% by weight or less than 10% by weight of the granules or the molded product, when containing a radical trapping agent such as 4-methoxyphenol. Preferably 1 to 5% by weight. In the case of producing granules or moldings by extrusion granulation, in order to improve the productivity by adjusting the viscosity, it is necessary to contain organic or inorganic salts such as sodium citrate, sodium sulfate and sodium tetraborate or as a grinding aid. When it contains aluminosilicate, such as 3-50 weight% in a granule or a molding, it is preferable, More preferably, it is 5-40 weight%. In the case of containing a radical trapping agent or an organic or inorganic salt, the content of the radical trapping agent or the organic or inorganic salt may be adjusted by adjusting the content of the binder compound as in the case of containing a surfactant.

In addition, in order to impart aesthetic appearance, in the case of containing a pigment or a dye, the content of the pigment or the dye may be adjusted in the same manner as the content of the binder compound.

The content of each component in the granules or moldings in the case of the bleach composition and the bleaching detergent composition comprising the granules or moldings containing (b) / (c-1) / binder compound is preferably 3 to 50% by weight / 3. It is -30 weight% / 20-94 weight%. More preferably, it is 5-30 weight% / 5-20 weight% / 50-90 weight%. When the component (b) exceeds the above range, granulation or molding may be difficult, or the strength of the granule or molding may be lowered so that the effect of granulation or molding may be less. Damage and discoloration of clothing by an ingredient may not be fully suppressed. In addition, the bleaching effect of the component (c-1) may not be increased even when the above range is exceeded, and damage or discoloration to clothing may be difficult, and a sufficient bleaching effect may not be obtained below the above range. . On the other hand, if the binder compound exceeds the above range, it takes a long time until the component (c-1) is dissolved, and not only a sufficient bleaching effect can be obtained, but also a large number of granules need to be blended into the molded product. Sometimes it becomes economic. In addition, below the said range, it may become difficult to granulate or shape.

In the case of the bleach composition containing granules or moldings containing (b) / (c-2) / binder compound, the content in the granules or moldings is preferably 3 to 20% by weight / 50 to 90% by weight / 7-30 weight%. More preferably, it is 5-15 weight% / 55-85 weight% / 10-30 weight%. Even if the content of the component (b) exceeds the above range, the effect of inhibiting the fading of clothing may be saturated. Moreover, below the said range, the fading inhibitory effect of clothing may be inadequate. In addition, the component (c-2) is preferably contained at a higher concentration than the component (c-1), and a sufficient bleaching effect may not be obtained below the above range, and the bleaching effect does not increase even if the above range is exceeded. There is a case.

On the other hand, when the binder compound exceeds the above range, it takes a long time until the component (c-2) is dissolved, not only a sufficient bleaching effect is not obtained, but also a large amount of granules need to be blended into the composition. Sometimes it becomes economic. In addition, below the said range, it may become difficult to granulate or shape.

In the bleach composition and the bleaching detergent composition in the present invention, it is preferable to use the component (c-1) and the component (c-2) together as the component (c) from the viewpoint of the bleaching power and the bactericidal power. In this case, in particular, the bleaching activating catalyst of the component (c-1) is a tris (salicylideniminoethyl) amine) -manganese complex, and the bleaching activating agent of the component (c-2) is 4-decanoyloxybenzoic acid or 4 It is preferable that it is sodium nonanoyloxybenzene sulfonate.

 The content of (b) component in the granules or moldings in the case of bleach compositions and bleaching detergent compositions comprising granules or moldings containing (b) / (c-1) / (c-2) / binder compounds , Preferably it is 3-50 weight%, More preferably, it is 5-30 weight%. When the content of the component (b) exceeds the above range, granulation or molding may be difficult, the strength of granules or moldings may be lowered, and the granulation or molding effect may be less. In addition, below the said range, the damage and discoloration of clothing by (c-1) component and (c-2) component may not be fully suppressed. Moreover, as for the total content of (c-1) component and (c-2) component in a granule or a molding, 3 to 90 weight% is preferable, 5 to 70 weight% is more preferable, and (c-1) It is preferable that the content rate of a component and (c-2) component is 1 / 2-1 / 7. Even if the total content of the component (c-1) and the component (c-2) exceeds the above range, the bleaching effect may not increase, and the clothing of the component (c-1) or the component (c-2) may Inhibition of damage or discoloration may be insufficient. If it is less than the said range, sufficient bleaching effect may not be acquired. Moreover, from the viewpoint of the bleaching effect and the sterilizing effect, the content ratio of the component (c-1) and the component (c-2) is preferable. As for content of a binder compound, 5-94 weight% is preferable from a viewpoint of productivity, shape maintenance, and solubility, More preferably, it is 10-90 weight%.

Component (d) of the present invention is a surfactant. It is preferable that surfactant of (d) component is essential about a bleaching detergent composition, and is included about a bleaching composition. As surfactant, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types as appropriate.

As anionic surfactant, the following are mentioned, for example:

(1) A straight or branched chain alkylbenzenesulfonic acid salt having an alkyl group having 8 to 18 carbon atoms (LAS or ABS).

(2) Alkanesulfonates having 10 to 20 carbon atoms.

(3) C10-C20 alpha-olefin sulfonic acid salt (AOS).

(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(5) a straight chain having 10 to 20 carbon atoms, in which 0.5 to 10 moles of either 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) are added; or Alkyl (or alkenyl) ether sulfate (AES) having a branched alkyl (or alkenyl) group.

 (6) a straight chain having 10 to 20 carbon atoms in which 3 to 30 moles of an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and a propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) are added on average; Alkyl (or alkenyl) phenyl ether sulfates having branched alkyl (or alkenyl) groups.

(7) straight or branched chain having 10 to 20 carbon atoms, in which 0.5 to 10 moles of 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) are added; Alkyl (or alkenyl) ether carboxylate having an alkyl (or alkenyl) group.

(8) Alkyl polyhydric alcohol ether sulfates, such as alkyl glyceryl ether sulfonic acid of 10 to 20 carbon atoms.

(9) C8-20 saturated or unsaturated α-sulfofatty acid salts or methyl, ethyl or propyl esters thereof (α-SF or MES).

(10) long-chain monoalkyl, dialkyl or seskialkyl phosphates.

(11) polyoxyethylene monoalkyl, dialkyl or seskialkyl phosphates.

(12) C10-20 higher fatty acid salt (soap).

Such anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts, ammonium salts and the like. These anionic surfactants can also be used as mixtures.

Examples of the anionic surfactant include alkali metal salts of linear alkylbenzenesulfonic acid (LAS) (for example, sodium or potassium salts), alkali metal salts of AOS, α-SF, AS, AES (for example, sodium or potassium salts), And alkali metal salts of higher fatty acids (for example, sodium or potassium salts).

The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used. As a nonionic surfactant, the following is mentioned, for example.

(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 to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. One polyoxyalkylenealkyl (or alkenyl) ether. Especially, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. As an aliphatic alcohol used here, a primary alcohol or a secondary alcohol is mentioned. Moreover, the alkyl group may have a side chain. As the aliphatic alcohol, primary alcohol is preferable;

(2) polyoxyethylene alkyl (or alkenyl) phenyl ethers;

(3) Fatty acid alkyl ester alkoxylates represented by the following formula (3) in which alkylene oxide is added between ester bonds of long-chain fatty acid alkyl esters:

R ⁹ CO (OA) _n OR ¹⁰ ... (3)

In the formula, R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an addition of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide or propylene oxide. Unit, n represents an average added mole number of alkylene oxide, generally 3 to 30, preferably 5 to 20, and R ¹⁰ is a lower alkyl group which may have a substituent having 1 to 3 carbon atoms;

(4) fatty acid esters of polyoxyethylene sorbitan;

(5) fatty acid esters of polyoxyethylene sorbet;

(6) fatty acid esters of polyoxyethylene;

(7) polyoxyethylene cured castor oil;

(8) fatty acid esters of glycerin;

(9) fatty acid alkanoyl amides;

(10) polyoxyethylenealkylamines;

(11) alkylglycosides; And

(12) alkylamine oxides.

Among the aforementioned nonionic surfactants, ethylene oxide is used for polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl or alkenyl) ether having a melting point of 40 ° C. or lower and HLB of 9-16, and a fatty acid methyl ester. Fatty acid methyl ester ethoxylate added, fatty acid methyl ester ethoxypropoxylate added with ethylene oxide and propylene oxide to fatty acid methyl ester and the like can be suitably used. Moreover, these nonionic surfactant can be used 1 type or in combination of 2 or more types as appropriate.

In addition, the HLB of the nonionic surfactant in this invention is a value determined by the method of Griffin (Yoshida, Shindo, Ogaki, and Yamanaka, "New Edition Surfactant Handbook", Kogyo-Kiso Kabushiki Kaisha published. , 1991, page 234).

 In addition, melting | fusing point in this invention is the value measured by the freezing point measuring method described in JISK8001 "General Rule for Reagent Test Method."

The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used. As a cationic surfactant, the following are mentioned, for example:

(1) di-long chain alkyl di-short chain alkyl type quaternary ammonium salts;

(2) mono-long chain alkyl tri-short chain alkyl type quaternary ammonium salts; And

(3) tri-long chain alkyl mono-short chain alkyl type quaternary ammonium salts:

In the above, long-chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and short-chain alkyl is an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, benzyl group, or 2 to 4 carbon atoms, preferably 2 The hydroxyalkyl group or polyoxyalkylene group of -3 is shown.

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 1 type or in combination or 2 or more types as appropriate.

The content of the surfactant of component (d) contained in the bleaching detergent composition is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, even more preferably in the bleaching detergent composition in that it imparts sufficient cleaning performance. Is 15 to 35% by weight. Moreover, 50 weight% or more of surfactant total quantity is preferable, as for the total amount of anionic surfactant and a nonionic surfactant, 80 weight% or more is more preferable, 95 weight% or more is more preferable.

In the case of the bleach composition, the component (d) may further contain a surfactant used in the bleach detergent composition for the purpose of improving the solubility of the hydrophobic component (fragrance, etc.) in the bleach formulation, as well as in granules or moldings, and for improving the permeability to clothing. have. The content is preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight.

In the bleaching composition and the bleaching detergent composition of the present invention, various additives and the like may be blended, if necessary, in addition to the components (a), (b), (c) and (d). Specific examples are as follows.

(Ⅰ) Detergency Builder (builder)

In addition, other components included in the bleach composition and the bleach detergent composition include inorganic and organic detergent builders.

(I) -1 weapon Builder

Examples of the inorganic builders include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and sodium sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered sodium silicate (for example, manufactured by Clariant Japan Company). Crystalline alkali metal silicates such as [Na-SKS-6] (δ-Na ₂ O ₂ SiO ₂ ), amorphous alkali metal silicates, sulfates such as sodium sulfate and potassium sulfate, alkali metal chlorides such as sodium chloride and potassium chloride, or Phosphates such as borate, pyrroline, tripolyphosphate, metaphosphate, hexametaphosphate, and phytic acid salts, crystalline aluminosilicates, amorphous aluminosilicates, complexes of sodium carbonate and amorphous alkali metal silicates (for example, Rhodia's trade name [NABION15] ), And the like.

Of the inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate and aluminosilicate are preferred.

As aluminosilicate, both crystalline and amorphous (amorphous) can be used, but crystalline aluminosilicate is preferable from the viewpoint of cation exchange capacity. As crystalline aluminosilicate, A type, X type, Y type, P type zeolite, etc. can be mix | blended suitably, As for an average primary particle diameter, 0.1-10 micrometers is preferable. The content of crystalline aluminosilicate is preferably 1 to 40% by weight of the bleaching detergent composition, and 2 to 30% by weight is particularly preferable in view of powder physical properties such as cleaning power and inducibility.

When the crystalline alkali metal silicate is blended in the bleaching detergent composition, 0.5 to 40% by weight is preferable, more preferably 1 to 25% by weight, more preferably 3 to 20% by weight, particularly preferably 5 to 15 It is preferable from a viewpoint of cleaning power to contain weight%.

(I) -2 organic Builder

Examples of the organic builders include aminocarboxylic acid salts such as nitrilo triacetate, ethylenediaminetetraacetic acid salt, β-alanine diacetate, aspartamic acid diacetate, methylglycine diacetate and imino disuccinate; Hydroxyaminocarboxylic acid salts such as serine diacetic acid salt, hydroxyiminodisuccinate salt, hydroxyethylethylenediamine triacetate salt, dihydroxyethylglycine salt and the like; Cyclocarboxylic acid salts such as pyromellitate, benzopolycarboxylate and cyclopentane tetracarboxylate; Ether carboxylic acid salts such as carboxymethyl tartronate, carboxymethyloxy succinate, oxy disuccinate and tartaric acid mono or disuccinate; Acrylic polymers and copolymers such as polyacetal carboxylates such as polyacrylic acid salts, polyacrylic acid, acrylic acid-allyl alcohol copolymers, acrylic acid-maleic acid copolymers, polyglyoxylic acids, hydroxyacrylic acid polymers, and polysaccharide-acrylic acid copolymers; Polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid and aspartamic acid; Polysaccharide oxides such as starch, cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethyl cellulose.

Among these organic builders, citrates, aminocarboxylates, hydroxyaminocarboxylates, polyacrylates, acrylic acid-maleic acid copolymers, polyacetalcarboxylates are preferred, especially hydroxyiminodisuccinates, molecular weights of 1000 to 80000. Salts of the acrylic acid-maleic acid copolymer, polyacrylates or polyacetal carboxylates such as polyglyoxylic acids having a molecular weight of 800 to 1,000,000, preferably 5000 to 200,000, as described in JP-A-54-52196 are suitable. . The content of the organic builder is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 5% by weight in the bleaching detergent composition.

Detergent builder can be used 1 type or in combination of 2 or more types as appropriate. Organic builders such as citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer, polyacetal carboxylate, zeolites, etc. It is preferable to use a weapon builder. The content of the detergency builder is preferably 10 to 80% by weight, more preferably 20 to 75% by weight in the bleaching detergent composition to impart sufficient detergency.

(II) pH adjuster

Although the pH of the bleach composition and the bleach cleaner composition of the present invention is not particularly limited, the pH of the bleach composition and the bleaching detergent composition is increased in a 1% by weight aqueous solution in order to increase the effect of inhibiting fading and fading of clothing caused by water-insoluble or poorly water-soluble fiber powder. It is preferable to adjust so that it may be 8 or more, and it is preferable that pH is 9-11 in 1 weight% aqueous solution. Below this range, the bleaching effect may not be sufficient.

As a technique for controlling pH, pH adjustment is usually performed by an alkali agent, and in addition to the alkali agent described in the above-mentioned cleaning builder, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, and the like are used. These can be used and these can be used 1 type or in combination or 2 or more types as appropriate. From the standpoint of solubility in water and alkalinity, it is preferable to use NABION15 (manufactured by Rhodia Company), which is a mixture of sodium carbonate, sodium silicate and water at a 55/29/16 ratio.

In addition, in order to prevent the pH from becoming too high, an acid or the like may be used to adjust the range of the pH. As an acid, the metal ion trapping agent mentioned later can also be used. In addition, an alkali metal phosphate dihydrogen salt such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid or polycarboxylic acid, citric acid, sulfuric acid, hydrochloric acid and the like can be used. In addition, a buffer may be used to prevent a drop in pH due to an acid component resulting from contamination of the garment during washing.

The bleach composition and the bleach cleaning composition of the present invention may contain a metal ion trapping agent, a boron compound, and a phenolic radical trapping agent, as necessary, in order to enhance the bleaching effect and the effect of suppressing damage and discoloration of clothes.

(III) metal ions Capture agent

The metal ion trapping agent traps trace metal ions and exhibits an effect of increasing the stability of hydrogen peroxide during storage and the stability of hydrogen peroxide in the bleaching treatment liquid.

 As a metal ion trapping agent, Amino polyacetic acids, such as ethylenediamine tetraacetic acid, nitrilo triacetic acid, glycol ethylenediamine hexaacetic acid, in addition to what is contained in the above-mentioned cleaning builder; 1-hydroxyethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2 -Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyl Organic phosphonic acid derivatives and salts thereof such as iminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid); Organic acids such as diglycolic acid, citric acid, tartaric acid, oxalic acid and gluconic acid and salts thereof. Among them, 1-hydroxyethane-1,1-diphosphonic acid disodium (HEDP-2Na), 1-hydroxyethane-1,1-diphosphonic acid trisodium (HEDP-3Na) and 1-hydroxyethane-1 Sodium, 1-diphosphonic trisodium (HEDP-4Na) and sodium ethylenediaminetetra (methylenephosphonic acid) are preferred, and considering the effects on bleaching power and storage stability in the bleach composition and the bleach detergent composition, 1-hydride More preferred are hydroxyethane-1,1-diphosphonic acid tetrasodium (HEDP-4Na) and sodium citrate. These metal ion scavengers are preferably surfactants or polyethylene glycol 1000-20000 (cosmetic) to suppress deliquescence and the like. As a granule by mixing with an average molecular weight of 500-19000 of the raw material standard (note 2) and a polyacrylic acid having a weight average molecular weight of 1000-1000000, its salt, (b) component, (c) component, film-forming polymer, etc. It can mix and use.

The preferable content of the metal ion trapping agent in the present invention is 0.1 to 5% by weight, more preferably 0.3 to 3% by weight in the bleach composition. If it is less than 0.1 weight%, the stabilizing effect of a peroxide may not be enough, and even if it exceeds 5 weight%, a stabilizing effect may not increase. Moreover, as a preferable content in a bleaching detergent composition, it is 0.1 to 5 weight%, More preferably, it is 0.5 to 3 weight%. If it is less than 0.1 weight%, it may be inadequate from a viewpoint of a bleaching power and a washing | cleaning power, and it may add more than 5 weight%, and the effect may not increase further. These metal ion trapping agents can be used 1 type or in combination of 2 or more types as appropriate.

(IV) Boron Compound

The bleaching composition and the bleaching detergent composition of the present invention may further enhance the bleaching effect by adding a boron compound, and at the same time, the boron compound may act on hydrogen peroxide and free metal to further increase the stability of hydrogen peroxide in the bleaching treatment liquid. Here, as the boron compound, compounds containing boron in the molecule, such as boric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, and ammonium tetraborate, can be used. Among these, sodium tetraborate is particularly suitable. It may be contained as a hydrate.

When blending a boron compound in the present invention, the bleach composition is preferably 20% by weight or less, more preferably 5% by weight or less, and when blended in the bleaching detergent composition, preferably 15% by weight or less, more preferably Is 3% by weight or less, and it is often difficult to obtain an improvement in the bleaching effect and an improvement in the stability of hydrogen peroxide even when the above range is exceeded. These boron compounds can be used 1 type or in combination of 2 or more types.

(V) phenolic Radical  Trap

In the present invention, when a phenolic radical trapping agent is contained and used in combination with the water-insoluble or poorly water-soluble fiber powder of the component (b), it exhibits a high effect of suppressing damage and fading of clothing, and the oxide of the phenolic compound Since coloring to clothes does not occur, it is more suitable. Examples of the phenolic radical trapping agent include compounds having phenolic hydroxyl groups, ester derivatives of phenolic hydroxyl groups, ether derivatives, and the like. More specifically, such compounds are cresol, thymol, chlorophenol, bromophenol, methoxyphenol, nitrophenol, hydroxybenzoic acid, salicylic acid, hydroxybenzenesulfonic acid, 2,6-di-t-butyl-p-cresol , Naphthol, pyrogallol, phenoxyethanol and the like.

Among these, more preferable compounds include GE Penketh, J. Appl. Redox unit (OP) ₀ described in Chem., Vol 7, pages 512-521 (1957). (25 degreeC) is a compound which is 1.25V or less, More preferably, it is a compound which is 0.75V or less. The lower limit of the redox potential (OP) ₀ (25 ° C) is not particularly limited, but considering the effect on the bleaching effect, as a lower limit of (0.P.) ₀ (25 ° C) of the redox potential, 0. About 60 Hz is preferable. When the redox potential is out of the above range, the stabilizing effect of hydrogen peroxide may not be sufficient. If the redox potential is too low, the bleaching power may decrease.

It is also particularly preferred that the radical trapping agent dissolve quickly even at small mechanical forces, such as when immersion bleaching is more effective, with a logP value of 3 or less, which is a hydrophobic variable exhibiting solubility. The hydrophobic variable here is generally used as a variable which shows the property of the target compound. In the logP value, P (distribution coefficient) 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 concentration in water ).

 Details regarding hydrophobic variables are described, for example, in "Region of Science" Vol. 122 (1979), page 73. As a measuring method of a partition coefficient, the flask shaking method, the thin layer chromatography method, the HPLC measuring method are known, but it can calculate by calculation using a variable from Ghose, Pritchett, Crimppen, etc. (J. Comp. Chem., 9, 80 (1998)).

In view of the redox potential and solubility, and stability of the radical trapping agent when coexisted with a peroxide, 4-methoxyphenol and 4-hydroxybenzoic acid are particularly preferable among the above compounds. As these phenolic radical trapping agents, 1 type, or 2 or more types can be used combining them suitably.

In the bleach composition and the bleach cleaner composition of the present invention, the phenolic radical trapping agent may be added in any amount, but in the case of the bleach composition, the preferred content is 0.001 to 1% by weight, more preferably 0.01 to 1% by weight And in the case of a bleaching detergent composition, the preferred content is 0.0001 to 1% by weight, more preferably 0.001 to 0.5% by weight. If it is less than the said range, the combined effect with (b) component may not be fully acquired, and even if it exceeds the said range, the damage or discoloration effect of clothing may not increase any more. Moreover, it is preferable that it is an amount less than the same weight% as component (b). Color (b) may cause coloring of clothing at the same weight or more as the component (b). The phenolic radical trapping agent is preferably present in the same particles as the component (b) and the component (c), so that damage or discoloration of clothing can be more effectively suppressed, and in that case, granules are also used for the same reason. It is preferable that it is a ratio of less than the weight% with the said (b) component in the inside.

The bleach composition and the bleach detergent composition of the present invention may contain, in addition to the above components, the following auxiliary components as necessary in a range not preventing the effects of the present invention.

(1) spices

As a fragrance | flavor, the component of Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2003-89800 can be used.

In addition, a fragrance composition is a mixture which consists of a fragrance component, a solvent, a fragrance stabilizer, etc. When the said fragrance composition is mix | blended with the bleach composition and the bleach detergent composition of this invention, the content is preferably 0.001-20 weight%, More preferably, 0.01-10 weight% among the bleach composition and the bleach detergent composition.

In the case of blending the perfume component in the bleach composition and the bleach cleaner composition of the present invention, the perfume component is mixed in the mixer with respect to the surfactant-containing particles or the finally obtained bleach composition and the bleach cleaner composition at the time of preparation of the surfactant-containing particles. It is preferable to use by spraying or dripping, and it is more preferable to use by spraying.

When mix | blending the said fragrance component with the bleach composition and the bleach cleaner composition of this invention, these fragrance components can be used by impregnating the said (b) component. By impregnation, the deterioration of the fragrance due to the peroxide is suppressed or the impregnated fragrance is gradually released, so that a constant aroma can be maintained even after long-term storage.

(2) pigment

In order to improve the appearance of the composition, various pigments can be used. Although dyes and pigments are mentioned as a pigment | dye used for a bleach composition and a bleaching detergent composition, Among these, a pigment is preferable from a viewpoint of storage stability, and it is especially preferable to have oxidation resistance, such as an oxide. Preferred compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue (ultramarine) pigments, bluish blue (iron blue) pigments, cyanine blue, cyanine green and the like. Moreover, it is preferable to granulate these pigment | dyes with a complex, and in this case, it is preferable to use what melt | dissolved or disperse | distributed the pigment | dye in binder compounds, such as polyethyleneglycol (PEG). As the blue imparting agent, an aqueous solution or dispersion of a blue pigment such as blue or a green pigment such as copper phthalocyanine is sprayed and granulated by spraying with sodium sulfate or sodium carbonate or the like, or sprayed onto the surfactant-containing particles or the bleaching composition and the bleaching detergent composition of the present invention. Can be used.

In addition, the pigment water dispersion obtained by heat treatment by adding about 0.1 to 5% by weight of a dye to the polymer resin suspension to the spherical resin particles obtained by radical emulsion polymerization in an aqueous dispersion system is also mentioned above. It can be suitably used as an emulsifier in the same manner as

When the said pigment component is mix | blended with the bleach composition and the bleach cleaner composition of this invention, about the surfactant containing particle | grains at the time of preparation of said surfactant containing particle | grains, or the bleach composition and bleach cleaner composition which can be finally obtained in a mixer, It is preferable to spray or use the aqueous solution or aqueous dispersion of a pigment component, and it is more preferable to spray and use.

Alternatively, the aqueous solution or the aqueous dispersion of the pigment component may be sprayed or dropped onto the surface thereof, or the sprayer may be used, while the surfactant-containing particles or the finally obtained bleach composition and the bleach cleaner composition are transferred to a belt conveyor.

(3) fluorescent brightener

The bleach composition and the bleach cleaner composition of the present invention include 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) as a fluorescent dye. Biphenyl salts, 2- (styrylphenyl) naphthothiazole derivatives, 4,4'-bis- (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) sulfonic acid derivatives, and the like. Include.

The brand names include WHITEX SA, WHITEX SKC (manufactured by Sumitomo Chemical Company Limited), CINOPEARL AMS-GX, CINOPEARL DBS-X, CINOPEARL CBS-X (manufactured by Ciba Specialty Chemicals), Lemonite CBUS-3B (manufactured by Chiaty Chemicals Company) Etc. can be illustrated. Among them, CINOPEARL CBS-X and CINOPEARL AMS-GX are more preferable, and their content is preferably 0.001 to 1% by weight. These may be used alone or in combination of two or more.

(4) enzyme

Examples of enzymes (originally enzymes that perform enzymatic action during the washing process) include hydrolases, oxidoreductases, lyases, transferases, and isomerases, if classified by enzyme reactivity. In the invention, any one can be applied. Especially preferred are proteases, esterases, lipases, nucleases, cellulases, amirases and pectinases and the like. Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, erastase, subtilisin, BPN, papain, bromelain, carboxypeptidase A and B, aminopeptase, aspara Guillopeptidase A, B, etc. are mentioned. Commercially available products include Savinase, Alkalase, Everlase, Kannase (manufactured by Novozymes A / S), API 21 (manufactured by Showa Denko), Maxacal, Maxapem (manufactured by Generncor Internationl), Japanese Unexamined Patent Publication No. 5-25492 And protease K-14 or K-16 described in the above. Examples of the cellulase include Cellzyme (manufactured by Novozymes A / S) and the cellulase described in claim 4 of JP-A-63-264699. Examples of amylases include commercially available Termamil, Duramyl (manufactured by Novozymes A / S), and the like. One or two or more enzymes may be used in combination. In addition, it is preferable to use the granules which were granulated as separate stable particles in a dry blended state to a detergent raw material (particles).

(5) enzyme stabilizer

The bleach composition and the bleach cleaner composition of the present invention can be formulated with calcium salts, magnesium salts, polyols, formic acid, boron compounds and the like as enzyme stabilizers. Among these, sodium tetraborate, calcium chloride and the like are more preferable, and the content is preferably 0.05 to 2% by weight in the composition. These can be used 1 type or in combination or 2 or more types as appropriate.

(6) other polymers

In the case of high density, polyethylene glycol having an average molecular weight of 200 to 200,000, acrylic acid polymer having a weight average molecular weight of 1000 to 100,000, and / or maleic acid polymer, or polyvinyl chloride to give recontamination preventing effect to hydrophobic fine particles as a binder or powder physical agent. Cellulose derivatives, such as alcohol and carboxymethylcellulose, can be mix | blended. In addition, a terephthalic acid and a copolymer or terpolymer of ethylene glycol and / or propylene glycol units may be blended as a fouling release agent, or polyvinyl pyrrolidone or the like may be blended in order to impart a desalting effect. In these, the polyethyleneglycol of the average molecular weights 1500-7000 is preferable, and as content, 0.05-5 weight% is preferable. These can be used 1 type or in combination or 2 or more types as appropriate.

(7) Caking inhibitor

As an anti-caking agent, para-toluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide, etc. can be mix | blended.

(8) antifoam

Examples of the antifoaming agent include conventionally known antifoaming agents of silicone / silica-based antifoaming agents, and these antifoaming agents are prepared by using the method described in the lower left corner of page 4 of JP-A-3186307 described below. It is also good as water. First, 20 g of a silicone (compound type, PS antifoaming agent) manufactured by Dow Corning Company is added and mixed to 100 g of MALTDEXTRIN (enzyme-modified dextrin) manufactured by Nippon Starch Chemical Company Limited to obtain a homogeneous mixture. Subsequently, 50% by weight of the homogeneous mixture obtained, 25% by weight of polyethylene glycol (PEG-6000, melting point 58 ° C) and 25% by weight of neutral anhydrous mirabilite were mixed at 70 to 80 ° C, and then Fuji Powder Company Limited was prepared. Granulation is obtained by granulation by means of one extrusion granulator (EXKS-1 type).

(9) reducing agent

Sodium sulfite, potassium sulfite and so on.

The bleach composition and the bleach detergent composition of the present invention are within a range that does not interfere with the effects of the present invention, and can be blended as necessary as long as it is a component generally blended into a detergent for clothes and a bleach.

In the composition of the present invention, 0.0001 to 1% by weight of the compound produced by the oxidation reaction of the phenolic radical trapping agent may be contained. Examples of these compounds include formic acid, acetic acid, glycolic acid, propionic acid, malonic acid, malic acid and oxalic acid.

The method of using the bleach composition and the bleach cleaner composition of the present invention is not particularly limited. However, if the composition is a bleach composition, it is added to a washing machine with a detergent so as to be 0.02 to 0.5% by weight of a solution to wash the laundry, or 0.02 to 2 A method such as immersing the laundry in a wt% solution is suitable, and in particular, the dipping time can be used by dipping in about 15 to 15 hours, preferably about 15 to 60 minutes. In the case of the bleaching detergent composition, a method such as washing the laundry by adding 0.02 to 0.2% by weight of the solution to the washing machine or immersing the laundry in the 0.02 to 2% by weight solution is suitable, and particularly, 5 to 20 minutes by adding to the washing machine. It can be suitably used for carrying out the washing.

The form of the bleach composition and the bleach cleaner composition of the present invention is a solid such as powder, granule, tablet, briquette, sheet or bar, more preferably powder. The manufacturing method of the bleach composition and bleach cleaning composition of this invention is not specifically limited, For example, as mentioned above, it can manufacture according to the conventional method of each form other than granulating or shape | molding the said component suitably as needed. In the case of commercialization, a container may be used in consideration of the availability and stability of each product, but it is particularly preferable to select a container having a low influence on the decomposition of peroxide by humidity and light.

The bleach composition and the bleach cleaner composition of the present invention are not particularly limited in the laundry and the method of use thereof. For example, the textile products such as clothes, fabrics, sheets and curtains, paper products such as wood pulp, tableware or glass, laundry baths, etc. Dirt, organic contamination, yellowing substances, contamination, fungi, and the like can be bleached on them in the same manner as conventional bleach compositions and bleach cleaning compositions.

(d) component and said (c) component may be mix | blended in the same granule, and may be set as separate granule, respectively. In particular, in the bleaching detergent composition of the present invention, from the standpoint of stability, the surfactant is preferably prepared as a particle separate from the components (a) and (c) as the surfactant-containing particles, and particularly, granules of the components (a) and (b) It is more preferable to prepare them as particles separate from the components (a), (b) and (c) except for the surfactant used as the base.

The method for producing a surfactant-containing particle suitable for use in the composition of the present invention can be broadly divided into two types: 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. have.

Surfactant-containing particles whose anionic surfactant is the main surfactant

In the present invention, the surfactant-containing particles having the anionic surfactant as the main surfactant are particles having the highest content of the anionic surfactant among the surfactant components blended in the particles as essential components of the anionic surfactant. Therefore, although other surfactants, such as nonionic surfactant, cationic surfactant, and amphoteric surfactant other than anionic surfactant, are restrict | limited in content, it can mix | blend suitably.

As nonionic surfactant used for surfactant containing particle | grains which make anionic surfactant the main surfactant, if it is conventionally used in washing | cleaning as illustrated as (d) component mentioned above, it will not specifically limit, Various anionic surfactant can be used Can be.

In the surfactant-containing particles containing the anionic surfactant as the main surfactant, the surfactant may be used in combination of one kind or two or more kinds of nonionic surfactants as the main surfactant.

As content of the total surfactant compound in surfactant containing particle | grains which make anionic surfactant a main surfactant, Preferably it is 10-90 weight% in surfactant containing particle | grains from a viewpoint which gives sufficient washing | cleaning performance, More preferably, it is 15-70 % By weight, more preferably 15 to 50% by weight. The weight ratio of the anionic surfactant / other surfactant is 100/0 to 50/50, preferably 100/0 to 55/45, and more preferably 95/5 to 70/30.

The surfactant-containing particles containing the anionic surfactant as the main surfactant can be used without particular limitations on the various additives and auxiliary components described above.

Among these, inorganic builders have a solubility-improving effect, and examples thereof include potassium salts such as potassium carbonate and potassium sulfate, and alkali metal chlorides such as potassium chloride and sodium chloride. Among them, alkali metal chlorides such as potassium carbonate, calcium chloride and sodium chloride are preferable from the viewpoint of the balance between solubility improvement effect and cost.

In the case of blending potassium carbonate, the content is preferably 1 to 15% by weight, more preferably 2 to 12% by weight, still more preferably 5 to 10% by weight in terms of solubility-improving effect.

When the alkali metal chloride is blended, the content thereof is preferably 1 to 10% by weight, more preferably 2 to 8% by weight, still more preferably 3 to 7% by weight in the surfactant-containing particles in view of the solubility-improving effect. .

The physical properties of the surfactant-containing particles, in which the nonionic surfactant is the main surfactant, are not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1.2 g / mL, and more preferably 0.6 to 1.1 g /. mL. The average particle diameter is preferably 200 to 1500 µm, more preferably 300 to 1000 µm. When the average particle diameter is less than 200 µm, dust may be easily generated, whereas when it exceeds 1500 µm, solubility may be insufficient. Also, the fluidity of the surfactant-containing particles is suitably 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. In addition, the angle of repose can be measured by the angle of repose measurement by a so-called discharge method, which measures an angle formed with the horizontal plane of the sliding surface formed when a satisfactory particle flows out into the container.

Surfactant containing particle | grains which make an anionic surfactant the main surfactant can be largely obtained by the following two methods.

(1) Method of Granulating Neutral Salt Type Anionic Surfactant

(2) Drying-neutralizing the acid precursor of the anionic surfactant to granulate

(1) In the method of granulating a neutral salt type nonionic surfactant, it can be obtained by the following granulation method.

(1-1) Extrusion granulation method of mixing and kneading the raw material powder and the binder compound (surfactant, water, liquid polymer component, etc.) of the detergent component and extruding and granulating, (1-2) mixing and kneading Mixing, crushing granulation method for crushing and granulating the obtained solid detergent, (1-3) stirring granulation method for granulating while adding a binder compound to the raw material powder and stirring with a stirring blade, (1-4) raw material powder Vibration granulation method which sprays and granulates a binder compound, vibrating, and (1-5) the fluidized-bed granulation method which sprays and granulates a liquid binder, while fluidizing a raw material powder.

(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, it is necessary to neutralize and granulate, but basically (1) neutralization The granulation method used in the method of granulating a salt type anionic surfactant can be used similarly suitably. Specific methods, devices, conditions and the like are as described above.

The acid precursor of a suitable anionic surfactant can be suitably used as long as the acid precursor of the anionic surfactant which can be suitably used mentioned above. Although it does not restrict | limit especially as alkaline powder as neutralization, Alkali metal carbonate, alkali metal silicate, alkali metal phosphate, etc. are mentioned. Examples of alkali metal carbonates include sodium carbonate, potassium carbonate, sodium bicarbonate, calcium hydrogen carbonate, sodium carbonate, potassium, and the like, and alkali metal silicates include sodium silicate, layered sodium silicate, and the like, and alkali metal phosphate sodium tripolyphosphate, Sodium pyrophosphate and the like. Of these, alkali metal carbonates are preferred, and sodium carbonate, potassium carbonate, sodium carbonate and potassium are particularly preferred. These can use 1 type (s) or 2 or more types.

Surfactant containing particle | grains which make the anionic surfactant granulated by the method mentioned above as a main surfactant can be classified as needed, and can be used for the product only of surfactant containing particle | grains of a desired particle size.

Surfactant-containing particles, wherein the nonionic surfactant is the main surfactant

In the present invention, the nonionic surfactant is a surfactant-containing particle which is a main surfactant, and means a particle containing a nonionic surfactant as an essential component and having the highest content of nonionic surfactant among the surfactant components blended in the particle. do. Accordingly, other surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants other than nonionic surfactants may be blended with limited contents.

As a nonionic surfactant, if it is conventionally used for detergent, it will not specifically limit, Various nonionic surfactant can be used. As a nonionic surfactant, the thing similar to what was illustrated to the above-mentioned (d) component can be used. As nonionic surfactant in surfactant containing particle | grains whose nonionic surfactant is a main surfactant, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl whose melting | fusing point is 40 degrees C or less and HLB are 9-16. Fatty acid methyl ester ethoxylate obtained by adding fatty acid methyl ester to (or alkenyl) ether, ethylene oxide, and fatty acid methyl ester ethoxypropoxylate obtained by adding fatty acid methyl ester to ethylene oxide and propylene oxide are preferred. In addition, other surfactants such as anionic surfactants, cationic surfactants and amphoteric surfactants may also preferably be the same as those listed in the above-mentioned component (d). The said surfactant can be used 1 type or in combination of 2 or more types suitably, A nonionic surfactant is used as a main surfactant normally, A nonionic surfactant is used 1 type or in combination of 2 or more types.

Since the content of the total activator compound in the surfactant-containing particles in which the nonionic surfactant is the main surfactant imparts sufficient washing performance, it is preferably 5 to 85% by weight, more preferably 10 to 60 in the surfactant-containing particles. Weight percent. Moreover, as a weight ratio of a nonionic surfactant / other surfactant, it is 100/0-50/50, Preferably it is 100/0-60/40, More preferably, it is 95/5-70/30.

Inorganic and organic cleaning builders are mentioned as other components contained in surfactant containing particle | grains whose nonionic surfactant is a main surfactant. As the cleaning builder, a cleaning builder which can be blended into the surfactant-containing particles containing the above-mentioned anionic surfactant as the main surfactant is equally available. The same applies to the content of a suitable cleaning builder and cleaning builder.

In addition, it is preferable to mix | blend an oil-absorbing carrier for carrying a nonionic surfactant, clay minerals as granulation manufacture, etc. in surfactant containing particle | grains whose nonionic surfactant is a main surfactant.

As the oil absorbent carrier, the oil absorption amount represented by the JIS-K5101 test method is preferably 80 mL / 100 g or more, and more preferably 150 to 600 mL / 100 g oil absorbent materials can be suitably used. As such an oil absorption carrier, the component of Unexamined-Japanese-Patent No. 5-125400 or Unexamined-Japanese-Patent No. 5-209200 is mentioned, for example.

Such oil-absorbing carriers can be used alone or in combination of two or more thereof. The oil-absorbing carrier is preferably 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 15% by weight in the surfactant-containing particles in which the nonionic surfactant is the main surfactant.

Especially as a clay mineral, it belongs to the smectite group, It is preferable that the crystal structure has a dioctahedral three-layered structure. The clay mineral that can be 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, more preferably. Is 0.2 to 1.5 g / mL.

As a specific example of such a clay mineral, the component of Unexamined-Japanese-Patent No. 9-87691 is mentioned.

The clay mineral is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight in the surfactant-containing particles whose nonionic surfactant is the main surfactant.

The surfactant-containing particles in which the nonionic surfactants used in the present invention are the main surfactants can be suitably used as the various additives and auxiliary components described above, which can be suitably blended into the surfactant-containing particles containing the anionic surfactant as the main surfactant. Can be.

Although the physical property value of surfactant containing particle | grains whose nonionic surfactant is a main surfactant is not restrict | limited, Usually, a bulk density is 0.3 g / mL or more normally, Preferably it is 0.5-1.2 g / mL, More preferably, it is 0.6-1.1 g /. mL. The average particle diameter is preferably 200 to 1500 µm, more preferably 300 to 1000 µm. If the average particle diameter is less than 200 µm, dust may be generated and become easy, while if it exceeds 1500 µm, solubility may be insufficient. Moreover, fluidity | liquidity of surfactant containing particle | grains is 60 degrees or less, especially 50 degrees or less as repose angle. When it exceeds 60 degrees, the handleability of particle | grains may deteriorate.

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

In the case where the surfactant-containing particles are used as described above, the bleach composition and the bleaching detergent composition of the present invention may be selected from the group consisting of surfactant-containing particles in which anionic surfactants are the main surfactant and / or surfactant-containing particles in which the nonionic surfactant is the main surfactant. It can manufacture by mixing components other than that.

The physical properties of the finally obtained bleach composition and bleach detergent composition are not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.4 to 1.2 g / mL, and more preferably 0.5 to 1.0 g / mL. The average particle diameter is preferably 200 to 1500 µm, more preferably 300 to 1000 µm. If the average particle diameter is less than 200 µm, dust may be easily generated, while if it exceeds 1500 µm, solubility may be insufficient. Moreover, the fluidity | liquidity of surfactant containing particle | grains is 60 degrees or less, especially 50 degrees or less as repose angle. When it exceeds 60 degrees, the handleability of a particle may deteriorate.

According to the present invention, it is possible to obtain an oxygen-based bleach composition or a bleaching detergent composition which can more efficiently suppress damage and discoloration of clothing and the like even under severe conditions at the time of misuse, and also have a high bleaching power without causing coloration. The bleaching detergent composition has excellent cleaning power.

Although an Example and a comparative example demonstrate this invention more concretely below, this invention is not restrict | limited by these examples. In addition, unless otherwise indicated in the following example, a composition "weight" shows the compounding quantity in the pure water content with respect to the composition of the detergent particle group of Table 12, Table 13, and the quantity of each component in a table | surface, and The table shows the actual compounding amount.

 <Bleach composition>

[Examples 1-35 and Comparative Examples 1-11]

According to the composition shown to Tables 1-3, the powder bleach composition of Examples 1-35 and Comparative Examples 1-11 was manufactured according to the conventional method of powder bleaching composition. About each bleach composition, the bleaching power, the damage | damage of clothing, coloring, and the fading of clothes were evaluated by the following method. The results are written together in Tables 1-3. The average particle diameter of the obtained powder bleach composition was 300-800 micrometers, and the bulk density was 0.7-1.10 g / mL.

Assessment Methods

(Ⅰ) Preparation of curry contaminated cloth

5 packs of retort curry (bon curry gold-medium hot (made by Otsuka Foods Company Limited), contents 200 g / 1 pack) heated in a boiling water for 5 minutes by filtration using a gauze to remove solids, and 25 x The curry solution was uniformly attached to the fabric while immersing five 30 cm plain weaving cotton cloth (# 100) for 30 minutes. The fabric was removed, rinsed with tap water until the color of the detergent solution disappeared, dehydrated, dried naturally, and then supplied to the experiment as a 5 x 5 cm test piece.

(II) bleaching power

The bleaching power test was done using the 5 contaminated cloths obtained above.

The powder bleach composition shown in Tables 1 to 3 prepared 200 mL of a test solution at a concentration of 0.5% by weight (prepared in 3 ° DH hard water using deionized water and calcium chloride at 25 ° C.), followed by immersion for 30 minutes, followed by tap water. 2 minutes and 1 minute dehydration were performed, and it air-dried at 25 degreeC for 12 hours.

The reflectances before and after cleaning the raw cloth and bleaching were measured using a filter of 460 nm with NDR-101DP manufactured by Denshoku, Japan. The cleaning bleaching power was determined by the following equation, and the bleaching performance was evaluated. Bleaching power was determined by the average value of the bleaching power for five contaminated cloths, and evaluated according to the following criteria.

[Evaluation standard]

X: Bleaching power is low compared with reference composition

(Triangle | delta): Bleaching power is equivalent or more 0% or more + less than 10% compared with a reference composition

○: Bleaching power is higher than the standard composition, + 10% or more and less than 15%

(Double-circle): Bleaching power is remarkably high compared with a reference | standard composition, + 15% or more

Reference composition: (25 ° C, 3 ° DH, soaked for 30 minutes)

Sodium percarbonate 50%, sodium carbonate 50% (bleaching power 45%)

(III) damage to clothing. coloring

About the powder bleach composition shown in Tables 1-3, damage and a coloring test were done with the following method.

A rayon white cloth (6 × 6 cm for JIS dyeing fastness test) was placed on a Petri dish (9 cm in diameter and 1.5 cm in height), and 2.5 g of the powder bleach composition shown in Tables 1 to 3 was placed thereon. (Same as above) was covered from above. Thereafter, 2.5 g of tap water at 40 ° C. was gently flowed from above, left at room temperature for 24 hours, then rinsed quietly to observe damage or staining of fabrics and evaluated according to the following criteria.

[Standard of damage of clothing]

1: A crack enters a gun and torn.

2: A small hole is made in the gun.

3: The gun becomes thinner and pulls torn.

4: The gun becomes thinner and pulls out a small hole.

5: A gun becomes thin, but it does not break or make a hole when it is pulled.

6: no damage to the gun can be seen

(Coloring indication)

X: with coloring

○: no coloring

(ⅠⅤ) Fading

About the powder bleach composition shown in Tables 1-3, the fading test was done with the following method.

6 x 6 cm of cotton cloth (# 100) dyed with Reactive Red 21 was placed on a Petri dish (9 cm in diameter and 1.5 cm in height), and 2.5 g of the powder bleach composition shown in Tables 1 to 3 was placed thereon. , The dye cloth in the same manner as above was covered from above. Thereafter, 2.5 g of tap water at 40 ° C. was gently flowed from above, left for 2 hours, rinsed quietly, and fading of the fabric was observed to evaluate the following criteria.

 [Standard of fading of clothing]

1: severely fading locally

2: locally fading

3: slightly fading overall

4: very little fading overall

5: No fading can be seen.

Granules or moldings of Tables 1 to 3 were prepared by the following method.

Granule  Or manufacture of moldings

Granules or moldings of the compositions shown in Table 5 (bleach activating catalysts, bleach activators are referred to later, but powders are shown in Table 4) were prepared as follows.

Regarding granules 1 to 17, melted polyethylene glycol (PEG6000) and other components were uniformly mixed at 70 ° C. using a kneader, and then cooled to room temperature (20 ° C.) while stirring to obtain a size of 1 mm to 5 cm. A solid was obtained. Subsequently, the solid was pulverized and granulated in a grinder to prepare granules having an average particle diameter shown in Table 5.

Regarding the granules 18 to 21, all the components of the composition shown in Table 5 were uniformly powder mixed, fed into an Extrude O-Mix EM-6 type manufactured by Hosokawa Micron, kneaded and extruded, and cut by a cutter. As a result, a pellet-shaped molded article 1 having a particle size of 0.8 mm phi and a length of 0.5 to 3 mm was obtained (mixing temperature 60 ° C, temperature 20 ° C after extrusion and cutting).

Subsequently, the molded article 1 was introduced into a FITZMILL DKA-3 type manufactured by Hosokawa Micron Co., Ltd., and ground to prepare granules 2 having an average particle diameter shown in Table 5.

As for the raw material used in Table 5, the same raw material as the abbreviated component of the bleach composition described below in Table 5 was used.

Molding-containing bleach composition

Subsequently, the bleach composition was prepared in the same manner as in Examples 28 to 35, using the above molded product (1) instead of the granules (2), and the evaluation was carried out to obtain the same results as in Examples 28 to 35.

In addition, the following were used for the component in the table | surface.

● Sodium percarbonate: manufactured by Mitsubishi Gas Kagaku Kabushiki Kaisha (trade name: SPC-Z, effective oxygen content: 10.9%, blended with sodium percarbonate / sodium carbonate / sodium bicarbonate = 77/3/20 for non-hazardous productization)

Coated sodium percarbonate: Sodium percarbonate coated with silicic acid and sodium borate (manufactured by Mitsubishi Gas Chemical Co., Ltd. (trade name: SPC-D, effective oxygen content 13.2%).

(powder)

● Powder 1: Powdered cellulose (trade name: Arbocel FD600 / 30, manufactured by Rettenmeyer)

● Powder 2: Silk powder (brand name: Idemitsu Silk powder K-50, Idemitsu petrochemical company make)

Powder 3: crystalline cellulose (trade name: Avicel PH-302, manufactured by Asahi Kasei Corporation).

● Powder 4: Carboxymethylcellulose Sodium (trade name: Daicel 1130, manufactured by Daicel Chemical Industries Limited)

● The solubility, average fiber length, or average particle diameter of Powders 1-4 are shown in Table 4. Solubility was solubility (g) with respect to 100g of 25 degreeC deionized water, and the measuring method of average particle diameter and average fiber length was measured according to the particle size test described in the Japanese Pharmacopoeia.

(Bleaching activation catalyst)

Catalyst 1: Tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] pentafluorophosphate. It is shown to the following formula. Synthesis was performed according to the Journal of the American Chemical Society 1998, Vol.

Catalyst 2: (tris (salicylideneiminoethyl) amine) -manganese complex. It is represented by the following formula. The synthesis method is shown below.

Catalyst 3: (N, N'-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex. It is represented by the following formula. The synthesis method is shown below.

 Catalyst 4: Tris ((2-pyridyl) methyl) amine manganese complex. It is represented by the following formula. The synthesis method is shown below.

 Catalyst 5: [13,14-dichloro-6,6-diethyl-3,4,8,9-detrahydro-3,3,9,9-tetramethyl-1H-1,4,8,11 -Benzotetraazacyclotridesine]-iron complex. It is represented by the following formula. It synthesize | combined according to the Example of the international patent application 2000-5151 published in Japan.

(Bleach activator)

Bleach activator 1: tetraacetylethylenediamine (a reagent prepared by Canto Chemical Company, Inc.)

Bleach activator 2: 4-decanoyloxybenzoic acid (a reagent manufactured by Mitsui Chemicals, Inc.)

Bleach activator 3: sodium 4-dodecanoyloxybenzenesulfonate. The synthesis method is shown below.

Bleach activator 4: 4-nonanoyloxybenzenesulfonate sodium. The synthesis method is shown below.

(Bleach activator granules)

Bleaching activator A: Tetraacetylethylenediamine granules (trade name: TAED 4049, Clariant Japan Limited, pure content: 86%), and the preparation method of the bleaching activators B to D are shown below.

● Sodium carbonate: Tokuyama Corporation make (brand name: soda ash DENSE)

● Sodium tetraborate: Sodium tetraborate, 5 beard (brand name: Neobor, Borax Inc. make)

NABION15: Alkali agent (made by Rhodia Japan Limited) which consists of a mixture of sodium carbonate, sodium silicate, and water of the ratio of mass ratio 55/29/16.

HEDP-4Na: 1-hydroxyethane-1,1-diphosphonic acid tetrasodium (manufactured by Solutia Japan Limited, trade name: DEQUEST 2016D).

Ethylene diamine tetra (methylenephosphonic acid) -Na: manufactured by ALBRIGHT & WILSON, (trade name: BRIQUEST (registered trademark) 422).

(Surfactants)

POE-AE (1): nonionic surfactant (alkyl chain length 12-14, ethylene oxide average added mole number 5, ethylene oxide 3-7 mole adduct more than 90% of the total. (Pure content: 90% ) Lion Corporation manufacture.

POE-AE (2): nonionic surfactant (alkyl chain length 12-15, ethylene oxide average molar number 15. (pure content: 90%) Lion Corporation manufacture.

LAS-Na: Neutralized linear alkyl (10-14 carbon atoms) benzenesulfonic acid (LIPOLAN LH-200 (LAS-H, pure content 96%) manufactured by Lion Corporation) with sodium carbonate.

Α-SF-Na: α-sulfofatty acid alkyl ester (2: 8 mixture of methyl ester (PASTELL M-14 and PASTELL M-16 (LION Oleochemical Co. Ltd.)) was carried out in Japanese Patent Application Laid-Open No. 2001-64248. Sulfonation and extraction after the esterification step according to the method described in Example 1 to prepare α-sulfofatty acid alkyl esters, which were then neutralized with sodium carbonate.

AOS-K: α-olefinsulfonic acid potassium (produced by Lion Corporation) having an alkyl group having 14 to 18 carbon atoms.

AOS-Na: Sodium α-olefin sulfonate having 14 carbon atoms (LIPOLAN PJ-400 manufactured by Lion Corporation).

 AS-Na: Sodium laurylsulfonic acid (the pure content of SLS, AS-Na manufactured by Nico Chemical Company Limited: 95.7%).

(enzyme)

Enzyme (1): manufactured by Novozymes A / S (trade name: Everlase 8.0T).

● Enzyme (2): manufactured by Novozymes A / S (trade name: Lipex)

(Spices)

Fragrance composition: Fragrance compositions A-D used the thing of Table 1-7 of Unexamined-Japanese-Patent No. 2003-89800.

(Radical trap)

4-methoxyphenol: Kawaguchi Chemical Industries, Ltd. (trade name: MQ-F).

BHT: di-t-butyl-hydroxytoluene, manufactured by Nikki-Universal Company Limited (trade name: BHT-C).

(Etc)

Sodium sulfate: manufactured by Shikoku Corporation (trade name: Neutral Anhydrous Mirabilite).

Sodium citrate: manufactured by Fuso Chemical Company Limited (trade name: Purified Sodium Citrate L).

PEG: Polyethylene glycol (brand name: PEG # 6000M, Lion Corporation).

Catalyst 2: Tris (salicylideneiminoethyl) amine )-manganese Complex  synthesis

Tris (2-aminoethyl) amine (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), salicylaldehyde (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), manganese chloride tetrahydrate (reagent, manufactured by Kanto Chemical Co., Ltd.), methanol (reagent) , Canto Chemical Company Limited) and ethanol (reagent, Amakusa Chemical Industries, Ltd.) were used as raw materials for the synthesis by the following method.

48.7 g (0.333 mol) of tris (2-aminoethyl) amine was charged to a reaction vessel, dissolved in 300 mL of methanol, and cooled to 0 ° C. To this, a solution in which 121.9 g (0.998 mol) of salicylaldehyde was dissolved in 100 mL of methanol was added dropwise over 1 hour. After completion of the dropwise addition, the solution was further stirred at 0 ° C. for 1 hour. After stirring was complete, the mixture was left at 0 ° C. for 3 hours and then precipitated yellow crystals were filtered using a Kiriyama funnel. The obtained crystals were recrystallized and purified using 500 mL of ethanol to obtain 143 g of tris (salicylideneiminoethyl) amine crystals.

1.Og (0.002 mol) of tris (salicylideneiminoethyl) amine crystal obtained above was dissolved in 100 mL of ethanol, and 0.43 g (0.002 mol) of manganese chloride tetrahydrate was added to this solution at room temperature. Ethanol was concentrated to about 50 mL under reduced pressure, and then left at 5 ° C for 24 hours. The precipitated dark green crystals were separated by filtration to obtain 1.1 g of crystals (catalyst 2) of the tris (salicylideneminoethyl) amine) -manganese complex.

Catalyst 3: (N, N'- Ethylene bis (4- Hydroxysalicylideneimide )-manganese Complex  synthesis

Ethylenediamine (Reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2,4-Dihydroxybenzaldehyde (Reagent, manufactured by Canto Chemical Company Limited), Manganese chloride tetrahydrate (Reagent, Canto Chemical Company Limited reagent), Methanol (Reagent It synthesize | combined by the following method using the canto chemical company limited reagent) and ethanol (reagent, the Amakase chemical company limited) as a raw material.

30.1 g (0.501 mol) of ethylenediamine was placed in a reaction vessel, dissolved in 300 mL of methanol, and cooled to 0 ° C. 138.1 g (1.000 mol) of 2,4-dihydroxybenzaldehyde was dissolved in 100 mL of methanol and added dropwise to the solution over 1 hour. After completion of the dropwise addition, the solution was stirred at 0 ° C. for 1 hour. After stirring was complete, the mixture was left at 0 ° C. for 3 hours, and the precipitated yellow crystals were filtered using a Kiriyama funnel. The obtained crystals were recrystallized from 500 mL of ethanol and purified to give 135 g of crystals of N, N'-ethylenebis (4-hydroxysalicylideneiminate). Crystals of N, N'-ethylenebis (4-hydroxysalicylideneiminate) 1.Og (0.003 mol) was dissolved in 100 mL of ethanol, and 0.66 g (0.003 mol) of manganese chloride 4 beard was added to this solution at room temperature. Added at. Ethanol was concentrated to about 50 mL under reduced pressure, and then left at 5 ° C for 24 hours. The precipitated brown crystals were separated by filtration to obtain 1.0 g of (N, N'-ethylenebis (4-hydroxysalicylideneiminate) -manganese complex (catalyst 3) crystals.

Catalyst 4: Tris ((2-pyridyl) methyl) amine -manganese Complex  synthesis

2- (chloromethyl) pyridine hydrochloride (reagent, manufactured by Sigma-Aldrich Corporation), 2,2'-dipicolylamine (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.), manganese chloride tetrahydrate (reagent, canto chemical company limited) Production), 5.4 N sodium hydroxide (prepared using sodium hydroxide (reagent, manufactured by Canto Chemical Company), diethyl ether (prepared reagent, manufactured by Canto Chemical Company), and ethanol (reagent, amarica chemical) The ligand (tris (2-pyridyl) methyl) amine was synthesize | combined according to the Example of Unexamined-Japanese-Patent No. 10-140193, using industry manufacture) as a raw material.

1.0 g (0.003 mol) of the obtained ligand crystal was dissolved in 100 mL of ethanol and 0.68 g (0.003 mol) of manganese chloride tetrahydrate were added to the solution at room temperature. The ethanol was concentrated under reduced pressure until about 50 mL remained, and then left at 5 ° C. for 24 hours. The precipitated crystals were separated by filtration to obtain 1.1 g of crystals (catalyst 4) of (tris (2-pyridyl) methyl) amine) -manganese complex.

Bleach Activator 3: Synthesis of 4- dodecanoyloxybenzenesulfonate sodium

sodium p-phenolsulfonic acid (reagent, manufactured by Canto Chemical Company, Inc.), N, N-dimethylformamide (reagent, manufactured by Canto Chemical Company, Inc.), lauric chloride (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) And acetone (reagent, manufactured by Canto Chemical Co., Ltd.) as raw materials, and synthesized by the following method.

100 g (0.46 mol) of previously dehydrated p-phenolsulfonic acid sodium sulfate was dispersed in 300 g of dimethylformamide, and lauric chloride was added dropwise at 50 DEG C over 30 minutes while stirring with a magnetic stirrer. After completion of the dropwise addition, the reaction was further performed for 3 hours, and then dimethylformamide was distilled off at 100 ° C under reduced pressure (0.5-1 mmHg). After washing with acetone, it was recrystallized with water / acetone = 1/1 (molar ratio) solvent. Yield 90%.

Bleach Activator 4: 4- Nonanoyloxybenzenesulfonic acid  Synthesis of Sodium

Sodium p-phenol sulfonate (reagent, manufactured by Canto Chemical Company, Inc.), N, N-dimethylformamide (reagent, manufactured by Canto Chemical Company, Inc.), chlorinated chloride (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) And acetone (reagent, manufactured by Canto Chemical Co., Ltd.) as raw materials, and synthesized by the following method.

100 g (0.51 mol) of previously dehydrated p-phenolsulfonic acid sodium sulfate was dispersed in 300 g of N, N-dimethylformamide, and 90 g (0.51 mol) of chloral chloride chloride was stirred at 50 DEG C while stirring with a magnetic stirrer. Dropwise added over minutes. After completion of the dropwise addition, the reaction was further performed for 3 hours, and then N, N-dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5-1 mmHg). After rinsing with acetone, recrystallization and purification with water / acetone = 1/1 (molar ratio) solvent gave 146 g of sodium nonanoyloxybenzenesulfonate crystals.

Bleach activator method for producing a granulated water B:

70 parts by weight of 4-decanoyloxybenzoic acid (manufactured by Mitsui Chemicals, Inc.) of bleach activator 2 as a bleach activator, PEG (polyethylene glycol # 6000M (manufactured by Lion Corporation)) 20 parts by weight, α- having 14 carbon atoms Sodium olefin sulfonate powder product (LIPOLAN PJ-400) (manufactured by Lion Corporation) was supplied to Extrude O-Mix EM-6 type manufactured by Hosokawa Micron Co., Ltd. in a ratio of 5 parts by weight, and kneaded and extruded (kneading temperature 60 ° C) A noodle-shaped extruded product having a diameter of 0.8 mm was obtained by introducing the extruded product (cooled to 20 ° C. by cold air) into a FITZMILL DKA-3 type manufactured by Hosokawa Micron, and 5 parts by weight of type A zeolite powder as a supplementary preparation. The same feeding and pulverization gave Bleaching activator granule B having an average particle diameter of about 700 mu m.

Method for producing a bleaching activator granule C water

A bleach activator granule C was prepared in the same manner as the bleach activator granule B, except that 4-dodecanoyloxybenzenesulfonate sodium of the bleach activator 3 was used as the bleach activator.

Bleach activator Granule  D manufacturing method

A bleach activator granule D was prepared in the same manner as the bleach activator B granules except that 4-nonanoyloxybenzenesulfonate sodium of the bleach activator 4 was used as the bleach activator.

[Examples 36-113 and Comparative Examples 12-35]

Depending on the composition shown in Tables 6 to 11 below, one or two selected from the surfactant-containing particle groups A to L produced by the following method, percarbonates, powders, bleach activating catalysts, granules shown in Table 5, and the foregoing Bleach activator granules A to D, and other components are placed into a horizontal cylindrical electric mixer (cylinder diameter 585 mm, cylinder length 490 mm, clearance of 20 mm with the inner wall on the inner wall of the drum 131.7 L, baffle 45 mm high) baffle), and a bleaching detergent composition of Examples 36 to 113 and Comparative Examples 12 to 35 was obtained by electric mixing for 1 minute under conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. About each bleaching detergent composition, the bleaching power, the damage of clothing, coloring, the fading of clothing, and the washing power were evaluated by the following method. The results are written together in Tables 6 to 11.

Assessment Methods

(Ⅰ) Preparation of curry contaminated cloth

Same as described in the "Preparation of (I) Curry Stain" column of the bleach composition

 (II) Preparation of Bilirubin Contaminated Cloth

0.06 g of bilirubin (a reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dispersed and dissolved in 100 mL of chloroform. 0.14 mL of this solution was added dropwise to one sheet of 6 x 6 cm cotton cloth (full width # 20), dried naturally, and then shielded and left to stand at room temperature overnight to obtain a bilirubin contaminated cloth.

(III) bleaching power

  (1) Bleaching power for curry contaminated cloth (bleaching power 1)

A Terg-0-Tometer manufactured by U.S. Testing, was used, and 5 curry contaminated cloths (5 × 5 cm) obtained from the above (I) curry contaminated cloth preparation and knit cloth were added to control the bath ratio by 30 times. After adding 900 mL of water of a predetermined hardness and temperature (Dietz 3 ° DH (manufactured by dissolving calcium chloride in ion-exchanged water) at 25 ° C), 1.35 g of the bleaching detergent composition shown in Tables 6 to 11 was added thereto at 120 rpm. After 15 minutes of washing, it was rinsed with running water for 1 minute and then dehydrated and dried.

The reflectances before and after the original fabric and cleaning were measured using a filter of 460 nm with NDR-101DP manufactured by Nippon Denshoku Industries Company Limited, and bleaching performance was determined by the following equation to evaluate the bleaching performance. Bleaching power was determined based on the average value of the bleaching power for 5 contaminated cloths.

〔Evaluation standard〕

X: Bleaching power is low in comparison with reference composition

△: more than 0% and less than + 10% in bleaching power is equal or more than standard composition

○: Bleaching power is higher than standard composition and is less than 15% more than + 10%

◎: Bleaching power is remarkably high in comparison with reference composition, and is more than + 15%

Standard composition

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

(2) Bleaching power against bilirubin contaminated cloth (bleaching power 2)

A Terg-0-Tometer manufactured by U.S. Testing, was used, and 5 bilirubin contaminants (6 × 6 cm) obtained from the above-mentioned (II) bilirubin contaminant preparation and a knitted fabric were added to control the bath ratio by 30 times. After adding 900 mL of water at a predetermined hardness and temperature (Dietz 3 ° DH (manufactured by dissolving calcium chloride in ion-exchanged water) at 25 ° C), 0.6 g of the bleaching detergent composition shown in Tables 6 to 11 was added at 120 rpm. After washing for 10 minutes, rinsed with running water for 1 minute, and then dried dehydrated.

The reflectances before and after the original fabric and cleaning were measured using a filter of 460 nm with NDR-101DP manufactured by Nippon Denshoku Industries Company Limited, and bleaching performance was determined by the following equation to evaluate the bleaching performance. Bleaching power was determined based on the average value of the bleaching power for 5 contaminated cloths.

〔Evaluation standard〕

X: Bleaching power is low in comparison with reference composition

△: more than 0% and less than + 10% in bleaching power is equal or more than standard composition

○: Bleaching power is higher than standard composition and is less than 15% more than + 10%

◎: Bleaching power is remarkably high in comparison with reference composition, and is more than + 15%

Reference composition (25 degrees Celsius, 3 degrees DH, washing for ten minutes)

Sodium percarbonate 4%, surfactant-containing particle group A 94%, enzyme A 2% (bleaching power 45%)

(IV) damage and coloring of clothing

The bleaching detergent compositions shown in Tables 6 to 11 were subjected to damage and coloring tests in the same manner as the "(III) Damage and coloring of clothing" column of the bleach composition except for the bleaching detergent composition instead of the powder bleaching composition.

(V) fading

 The bleaching detergent compositions shown in Tables 6 to 11 were subjected to a fading test in the same manner as in the (IV) fading column of the bleaching composition, except that the bleaching cleaning composition was used instead of the powdered bleaching composition.

(VI) cleaning power

Using a Terg-0-Tometer manufactured by U.S. Testing, 10 artificial contaminants (manufactured by Hirano Oil & Fats Co., Ltd.) and knit were added to adjust the bath ratio to 30 times. After adding 900 mL of water at a predetermined hardness and temperature (Dietz 3 ° DH (prepared by dissolving calcium chloride in ion-exchanged water), 25 ° C), 0.6 g of the bleaching detergent composition shown in Tables 6 to 11 was added at 120 rpm. After washing for 10 minutes, rinsed with running water for 1 minute, and then dried dehydrated.

The cleaning power was determined by the Kubelka Munch formula shown in the table below.

 Kubelka Munch Formula:

Here, K / S = (1-R) ² / 2R, R are reflectances that can be measured using a colorimeter Σ-90 manufactured by Nippon Denshoku. And the evaluation of the washing | cleaning power was performed with the average value of ten test cloths. Evaluation criteria were set as follows.

[Standard of washing power]

◎: 75% or more

○: 50% or more and less than 75%

×: less than 50%

In addition, each particle | grain and detergent composition property, etc. were measured as follows. The results are written together in Tables 6-11.

(VII) Measurement of Average Particle Size

For each sample and its mixture, classify using nine stage sieves and receiving pans of mesh sizes 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 149 μm The operation was performed. The sorting operation involves laminating a sieve from the smallest sieve to the largest sieve in the receiving pan, placing 100 g / base sample from the top of the top 1680 μm sieve and covering the stopper with a Ro-Tap Sieve shaker ( 10 minutes of tapping: 156 times / minute, rolling: 290 times / minute) was then vibrated for 10 minutes, and the samples remaining on the respective sieves and receiving pans were collected for each mesh to measure the mass of the samples.

When the mass frequencies of the receiving pans and the respective sieves are integrated, the mesh of the first sieve whose mass frequency of integration is 50% or more is set to a micrometer, and the mesh of the sieve one step larger than a micrometer is set to b micrometer. The average particle diameter (mass 50%) was determined from the following formula by setting the mass frequency of the mass frequency from the receiving pan to the a micron sieve as c% and the mass frequency on the a micrometer sieve as d%.

Average particle size (by mass ^{50%) = 10 (50- (} cd) / (logb - loga) x logb)) / (d / logb - loga))

 (VIII) Measurement of bulk density

The bulk density of each sample and its mixture was measured according to JIS K3362.

Molding-containing bleach cleaner composition

A bleaching detergent composition was prepared in the same manner as in Examples 89, 93, 97, 99, 100, 106, and 113 except for using the molding (1) instead of the granulation (2) described in the preparation of the granulation or molding. The same evaluation results as in Example 89, 93, 97, 99, 100, 106, and 113 were obtained.

[Examples 114-158]

Tablet Bleach Detergent Composition

0.1 parts by weight of dipropylene glycol was sprayed onto 91.4 parts by weight of each of the bleaching detergent compositions of Examples 69 to 113, followed by 1.5 parts by weight of finely divided A zeolite and mixed for 30 seconds. In addition, 7 parts by weight of ARBOCEL TF30HG (manufactured by Rettenmeyer Company), which was a disintegrant, was added and mixed for 30 seconds to obtain a mixture before compression molding. The pre-compression molding mixture was compressed into a rotary tableting machine (FETTE PT3090 / TSC) equipped with 27 tableting dies (flat shape: annular, side shape: flat rim angle) having a diameter of 34 mm. Total load 20.0 g ± 0.1 g, preload 1 kN, main pressure 4-6 kN, rotor rotation speed 22 rpm, tableting capacity 600 tablets / min, tableting temperature 25 ℃, tablets weight 20 g, diameter 34 mm, thickness 16 A tablet bleach detergent composition of ˜18 mm was obtained (Examples 114-158).

The real pressure was adjusted to between 4 and 6 kN so that the tablet strength immediately after molding (the maximum stress until the tablet was broken by crushing it on a tablet strength meter (TD-75N manufactured by Okada Seiko Co., Ltd.)).

The bleaching power, damage to clothes, coloring, fading of clothes, and cleaning power were evaluated for each of the above tablet bleaching detergent compositions, and the same evaluation results as in Examples 69 to 113 were obtained.

The composition is shown to Table 12 and Table 13 below for the manufacturing method of surfactant containing particle group A-L in a table | surface.

Method for producing surfactant-containing particle group A

According to the composition shown in following Table 12, surfactant containing particle group A was manufactured by the following procedures.

First, water was put into the mixing tank with a jacket provided with a stirring device, and the temperature was adjusted to 60 degreeC. Surfactant and polyethyleneglycol (PEG6000) other than (alpha) -SF ((alpha)-sulfonic acid fatty acid methyl ester sodium) and a nonionic surfactant were added to this, and it stirred for 10 minutes. Subsequently, after adding the polymer and the optical brightener and stirring for 10 minutes, a part of powder A zeolite (zeolite A) (Type A zeolite for mixed addition of 2.0% equivalent (diagonal particle group, hereinafter)), 3.2% A significant amount of grinding A-type zeolite, 1.5% equivalent of surface-type zeolite for surface coating), sodium carbonate and potassium carbonate were added. After stirring for 20 minutes to prepare a spray drying slurry having a moisture content of 38%, using a countercurrent spray drying tower, spray drying under conditions of a hot air temperature of 280 ° C., average particle diameter of 320 μm, and bulk density of 0.30 g / mL And spray-dried particles of 5% of water (105 ° C., 2 hours of weight loss, the same below) were obtained.

On the other hand, a part of the nonionic surfactant (25% to α-sulfonic acid methyl ester sodium) in an aqueous slurry (25% water concentration) of α-sulfonic acid fatty acid methyl ester obtained by sulfonating and neutralizing a fatty acid ester as a raw material. ) Was added, and the resulting mixture was concentrated under reduced pressure with a thin film dryer until 11% of water was obtained, thereby obtaining a mixed concentrate of α-sulfonic acid fatty acid methyl ester sodium and a nonionic surfactant.

Continuous kneader (KRC-S4 type, manufactured by Kurimoto Limited) with dry particles and the above mixed concentrate, 2.0% equivalent of A-type zeolite, remaining nonionic surfactant and water except for 0.5% equivalent of spray addition Was added to the mixture and mixed under the conditions of a mixing capacity of 120 kg / h and a temperature of 60 ° C to obtain a surfactant-containing kneaded product. The surfactant-containing kneaded material was cut with a cutter while extruded using a pelleter double (EXDF JS-100 type, manufactured by Fuji Powder Company Limited) with a die having a hole diameter of 10 mm (the cutter circumferential speed was 5 m / s). A pellet-like surfactant-containing molded article of about 5 to 30 mm was obtained.

Subsequently, 3.2% equivalent amount of particulate A zeolite (average particle diameter: 180 µm) was added to the obtained pelletized surfactant-containing molded article as a grinding aid, and FITZMILL (DKA) disposed in three stages under coexistence with cold air (10 ° C, 15 m / s) -3, manufactured by Hosokawa Micron, Inc. (screen hole particle size: 1 stage / 2 stages / 3 stages = 12 mm / 6 mm / 3 mm, and rotational speed: 1 stage / 2 stages / three stages, 4700 rpm). Finally, with a horizontal cylindrical electric mixer (mixer with a cylinder diameter of 585 mm, cylinder length of 490 mm, 20 mm clearance with the inner wall on the drum inner wall of the vessel 131.7 L, and two baffles with a height of 45 mm), the filling rate is 30 vol. 1.5% of finely divided A-type zeolite was added under conditions of%, rotational speed of 22 rpm and 25 ° C., and 0.5% equivalent of non-ionic surfactant and perfume were sprayed, followed by electric rolling and surface modification for 1 minute to obtain surfactant-containing particles. .

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

Method for producing surfactant-containing particle group B

According to the composition shown in following Table 12, surfactant containing particle group B was manufactured in the following procedures.

First, water was put into the jacketed mixing tank with a stirring device, and the temperature was adjusted to 60 degreeC. Surfactant and polyethyleneglycol except the (alpha) -SF ((alpha)-sulfonic acid fatty acid methyl ester sodium) and a nonionic surfactant were added to this, and it stirred for 10 minutes. Subsequently, after stirring for 10 minutes by adding sodium (polymer A) of the acrylic acid / maleic acid copolymer, HIDS and the optical brightener, a part of the powder A zeolite (7.0% equivalent of the A-type zeolite for mixed addition, 3.2% A significant amount of Type A zeolite for grinding aid, excluding Type A zeolite for layered coating of 1.5%), sodium carbonate and potassium carbonate were added. After stirring for 20 minutes to prepare a spray drying slurry having a moisture content of 38%, using a countercurrent spray drying tower, spray drying under conditions of a hot air temperature of 280 ° C., average particle diameter of 290 μm, volume density of 0.32 g / mL, and moisture of 5 % Spray dried particles were obtained.

On the other hand, a portion of the nonionic surfactant (25% to α-sulfonic acid methyl ester sodium) in an aqueous slurry (25% water content) of α-sulfonic acid fatty acid methyl ester sodium obtained by sulfonating and neutralizing a fatty acid ester as a raw material. ) Was added, and the resulting mixture was concentrated under reduced pressure in a thin film dryer until 11% of water was obtained, thereby obtaining a mixed concentrate of α-sulfonic acid fatty acid methyl ester sodium and a nonionic surfactant.

The above-mentioned dry particles, this mixed concentrate, 7.0% equivalent of A-type zeolite, remaining nonionic surfactant and water except for 0.5% equivalent of spray addition, and a continuous kneader (KRC-S4 type, manufactured by Kurimoto Limited) ), And mixed under the conditions of a mixing capacity of 120 kg / h, a temperature of 60 ℃ to obtain a surfactant-containing kneaded material.

This surfactant-containing kneaded material was cut with a cutter while extruding using a pelleter double (EXDF JS-100 type, manufactured by Fuji Powder Company Limited) equipped with a die having a pore size of 10 mm (the cutter circumferential speed was 5 m / s). A pellet-containing surfactant-containing molded article of about 5 to 30 mm was obtained.

Subsequently, 3.2% equivalent amount of particulate A-type zeolite (average particle diameter 180 mu m) as a grinding aid was added to the surfactant-containing molded product per pellet, and arranged in three stages under coexistence with cold air (10 DEG C, 15 m / s). Grinding was carried out using FITZMILL (DKA-3, manufactured by Hosokawa Micron) (Screen hole particle diameter: 1 stage / 2 stage / 3 stage = 12 mm / 6 mm / 3 mm, number of revolutions: 1 stage / 2 stage / 3 stage) 4700 rpm). Finally, the horizontal cylindrical electric mixer (cylinder with a cylinder diameter of 585 mm, cylinder length of 490 mm, 20 mm clearance with the inner wall on the inner wall of the drum of the container 131.7L, two baffles of 45 mm in height), filling volume 30%, A 1.5% equivalent finely divided A-type zeolite was added at a rotational speed of 22 rpm and 25 ° C, and 0.5% equivalent of a nonionic surfactant and a fragrance were sprayed and subjected to surface modification for 1 minute to obtain surfactant-containing particles.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle group A, surfactant-containing particle group B (average particle diameter 550micrometer, volume density 0.86g / mL) Got.

Method for producing surfactant-containing particle group C

Among the compositions shown in Table 12, a nonionic surfactant, A-type zeolite for mixed addition of 2.0% equivalent amount, A-type zeolite for 3.2% equivalent amount grinding aid, A-type zeolite for 1.5% equivalent surface coating, and After dissolving or dispersing the ingredients except fragrance in water to prepare a slurry having a moisture content of 38%, using a countercurrent spray drying tower, spray drying at a condition of hot air temperature of 300 ° C., average particle diameter of 330 μm and a bulk density of 0.30 g / mL and 3% of the spray dried particles were obtained. Along with these dry particles, 2.0% equivalent of A-type zeolite, 0.5% equivalent of non-ionic surfactant and water, except for spray addition, were added to a continuous kneader (KRC-S4 type, manufactured by Kurimoto Limited), and mixed with each other. It mixed on 120 kg / h and the temperature of 60 degreeC conditions, and obtained surfactant containing kneaded material.

The surfactant-containing kneaded material was cut with a cutter while extruding using a pelleter double (EXDF JS-100 type, manufactured by Fuji Powder Co., Ltd.) with a die having a hole diameter of 10 mm (the cutter circumferential speed was 5 m / s). A pellet-like surfactant-containing molded article having a length of about 5 to 30 mm was obtained.

Subsequently, 3.2% equivalent amount of particulate A zeolite (average particle diameter: 180 µm) as a grinding aid was added to the obtained pellet-containing surfactant-containing molded article, and after being arranged in three stages in series under cold air (10 ° C, 15 m / s), FITZMILL ( It was pulverized using DKA-3, manufactured by Hosokawa Micron (screen hole particle diameter: 1 stage / 2 stages / 3 stages = 12 mm / 6 mm / 3 mm, and the number of revolutions: 1 stage / 2 stages / three stages) rpm). Finally, in a horizontal cylindrical transfer mixer (mixer having a cylinder diameter of 585 mm, cylinder length of 490 mm, 20 mm clearance with the inner wall on the inner wall of the drum of the container 131.7L, and two baffles of 45 mm in height), a filling rate of 30% by volume, A 1.5% equivalent finely divided A-type zeolite was added at a rotational speed of 22 rpm and 25 ° C, and 0.5% equivalent of a nonionic surfactant and a fragrance were sprayed and subjected to surface modification for 1 minute to obtain a surfactant-containing particle.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle group A, surfactant-containing particle group C (average particle diameter 540micrometer, volume density 0.77g / mL) )

Method for producing surfactant-containing particle group D

According to the composition shown in following Table 12, surfactant containing particle group D was manufactured in the following procedures.

First, water was put into the jacketed mixing tank with a stirring device, and the temperature was adjusted to 50 degreeC. Sodium sulfate and the optical brightener were added to this, and it stirred for 10 minutes. Subsequently, after adding sodium carbonate, the acrylic acid / maleic acid copolymer sodium salt and ASDA were added, and after stirring for 10 minutes, sodium chloride and a part of powder A zeolite were added. And stirring for 30 minutes to prepare a spray drying slurry.

The temperature of the obtained spray drying slurry was 50 degreeC. The slurry was spray dried with a countercurrent spray dryer equipped with a pressure spray nozzle to obtain spray dried particles having a water content of 3%, a bulk density of 0.50 g / mL, and an average particle diameter of 250 µm.

Apart from this, a nonionic surfactant, polyethylene glycol, and anionic surfactants (LAS-Na, AS-Na, α-SF-Na, and soap) were mixed at 80 ° C. under a water content of 10% by weight of the surfactant composition. Was prepared. LAS-Na was used as a solution neutralized with an aqueous sodium hydroxide solution.

The spray-dried particles thus obtained were placed in a Lodige mixer (M20 type, manufactured by Matsubo Corporation) having a fork shovel and having a clearance between the shovel walls of 5 mm (filling rate of 50% by volume), and the jacket at 80 ° C. Stirring of the spindle (150 rpm) and the chopper (4000 rpm) was started while flowing hot water at a flow rate of 10 L / min. The surfactant composition prepared above was added over 2 minutes, followed by stirring for 5 minutes, followed by addition of a layered silicate (SKS-6, average particle diameter of 5 μm) and a part of the powder A-type zeolite (equivalent to 10%). By stirring for a minute, surfactant-containing particles were obtained.

The obtained surfactant-containing particles and 1 part (2% equivalent) of the powder A-type zeolite were mixed in a V blender, sprayed with a perfume, and then the same as the surfactant-containing particle group A in order to color a part of the surfactant-containing particles. The 20% aqueous dispersion of pigment | dye was sprayed by the method, and surfactant group D (average particle diameter 300 micrometers, volume density 0.75 g / mL) was obtained.

Method for producing surfactant-containing particle group E

In the composition shown in Table 12, after preparing a slurry having a moisture content of 38% by dissolving or dispersing components other than 5.0% of an A-type zeolite for surface coating, polyethylene glycol, layered silicate, pigment, and perfume in water, It spray-dried on the conditions of the hot air temperature of 300 degreeC using the type | mold spray drying tower, and obtained the spray drying particle | grains of an average particle diameter of 320 micrometers, a bulk density of 0.36 g / mL, and moisture of 3%. The spray-dried particles were put into a Lodige mixer (type M20, manufactured by Matsubo Corporation) having a fork shovel and a clearance between the shovel walls (5 mm, manufactured by Matsubo Corporation), and stirred at a spindle of 200 rpm and a chopper of 200 rpm. Started. 30 seconds after the start of stirring, polyethylene glycol and water warmed to 60 ° C. were added for 2 minutes, and stirring granulation was continued under the condition of a jacket temperature of 30 ° C. until the average particle diameter reached 400 μm.

Finally, layered silicate (SKS-6, 5 µm in average particle diameter) and 5.0% of finely divided A-type zeolite were added, stirred for 1 minute, surface-modified, and sprayed with perfume to obtain surfactant-containing particles.

In order to color a part of the obtained surfactant-containing particles, the surfactant-containing particles were transferred to a belt conveyor at a speed of 0.5 m / s (layer height of the surfactant-containing particles on the belt conveyor 30 mm, layer width 300 mm) on the surface thereof. A 20% aqueous dispersion of the dye was sprayed to obtain a surfactant-containing particle group E (average particle size 400 µm, bulk density 0.78 g / mL).

Method for producing surfactant-containing particle group F

According to the composition shown in following Table 12, surfactant containing particle group F was manufactured in the following procedures. First, water was put into the jacketed mixing tank with a stirring device, and the temperature was adjusted to 60 degreeC. After preparing a slurry of 38% moisture in which components other than the A-type zeolite, sodium carbonate, pigments and fragrances were dissolved or dispersed in water, spray drying was carried out using a countercurrent spray drying tower under a hot air temperature of 300 ° C. to obtain an average particle diameter of 280. Spray-dried particles of 탆, bulk density of 0.32 g / mL, and moisture of 6% were obtained.

On this, a horizontal cylindrical electric mixer (cylinder having a cylinder diameter of 585 mm, a cylinder length of 490 mm, a clearance of 20 mm with the inner wall surface and 22 baffles having a height of 45 mm on the drum inner wall of the container 131.7 L), a filling rate of 30% by volume, and rotation A fine powder A zeolite and sodium carbonate were added under water at 22 rpm and 25 ° C., and the mixture was surface-modified by electrophoresis for 1 minute while spraying the fragrance to obtain surfactant-containing particles.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle | grain group A, surfactant-containing particle group F (average particle diameter 350micrometer, volume density 0.48 g / mL) )

Method for producing surfactant-containing particle group G

According to the composition shown in Table 12, surfactant containing particle group G was manufactured in the same procedure as the method which manufactured surfactant containing particle group F, and surfactant containing particle group G (average particle diameter 350micrometer, volume density 0.50g / mL) )

Method for producing surfactant-containing particle group H

In the composition shown in the following Table 12, all raw materials (temperature 25 degreeC) except a 5.0% equivalence P-type zeolite (zeolite B), pigment | dye, and a fragrance used for surface coating are equipped with a fork shovel. Then, the clearance between the shovel walls was placed in a Lodige mixer (M20 type, manufactured by Matsubo Corporation) having a clearance of 5 mm (filling rate of 50% by volume), and stirring of the spindle 200 rpm and the chopper 200 rpm was started. 30 seconds after the start of stirring, the surfactant mixture (the nonionic surfactant and the anionic surfactant were previously heated to 60 ° C. and uniformly mixed) and water (temperature 60 ° C.) were added for 2 minutes, and the jacket temperature of 30 ° C. was added. Stirring granulation was continued on conditions until it became an average particle diameter of 400 micrometers. Finally, a 5.0% equivalent amount of P-type zeolite (zeolite B) was added, stirred for 30 seconds, surface modified, and sprayed with perfume to obtain surfactant-containing particles.

In order to color a part of obtained surfactant-containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant-containing particle group A, and surfactant-containing particle group H (average particle diameter 400micrometer, volume density 0.80g / mL) )

Method for producing surfactant-containing particle group I

Among the compositions shown in Table 13 below, a fluorescent brightener, potassium carbonate, and sodium carbonate pulverized product (compounding sodium carbonate with an average particle diameter of 30 µm in a table mill pulverizer (made of Stadmill 63C, manufactured by Alpine Industries AG)) The powder raw material (except the coating agent) was added to the fluidized bed (Glatt-POWREX, Powderex, Model No. FD-WRT-20) with a mass having a thickness of 200 mm at the time of standing. Thereafter, wind (air) at 20 ° C. was sent into the fluidized bed, and after confirming that the powder was fluidized, α-SF-H (sulfonic acid fatty acid alkyl ester) was sprayed from the top toward the fluidized bed. The air velocity in the fluidized bed was granulated while adjusting the fluidization state in the range of 0.2 to 2.0 m / s.

(alpha) -SF-H sprayed at 60 degreeC, and the nozzle for spraying used the 2-fluid hollow cone nozzle of the spray angle of 70 degrees. The spray rate was about 400 g / min. After the completion of spraying of α-SF-H, wind (air) at 20 ° C. was further sent into the fluidized bed and aged for 240 seconds. In addition, the granules were discharged from the fluidized bed and covered with 4.5% equivalent of the A-type zeolite in an electric drum (equipped with 4 baffles having a diameter of 0.6 m, a length of 0.48 m, a thickness of 1 mm X width of 12 cm X length of 48 cm, and a rotation speed of 20 rpm). It was.

Thereafter, 35% hydrogen peroxide aqueous solution (4.7% large particles) was added to the obtained particles by an electric drum (0.6 m in diameter, 0.48 m in length, 1 mm in thickness, 12 cm in width, 4 baffle plates of 48 cm in length, and 20 rpm). After spraying in-bleaching, it was also coated with 5.0% equivalent of the A-type zeolite for the improvement of fluidity, and sprayed the fragrance.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle group A, Surfactant containing particle group I (average particle diameter: 380 micrometers, volume density 0.50 g / mL) )

Method for producing surfactant-containing particle group J

Among the compositions shown in Table 13 below, components other than nonionic surfactants, 4.2% equivalent of grinding aid and 2.0% equivalent of surface-type zeolite, montmorillonite, white carbon, pigments and flavorings were dissolved or dispersed in water. After preparing a slurry having a water content of 40%, spray drying was carried out using a countercurrent spray drying tower under a hot air temperature of 300 ° C. to obtain spray dried particles having an average particle diameter of 300 μm, a bulk density of 0.45 g / mL, and a moisture of 3%. . With this dry particle, montmorillonite, white carbon, nonionic surfactant and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Limited), and mixed under conditions of a mixing capacity of 120 kg / h and a temperature of 60 ° C. Then, surfactant containing kneaded material was obtained.

The surfactant-containing kneaded material was cut with a cutter (5 m / s in cutter speed) while being extruded using a pelleter double (EXDF JS-100 type, manufactured by Fuji Powder Co., Ltd.) with a die having a hole diameter of 10 mm. A pellet-like surfactant-containing molded article of about-30 mm was obtained.

Subsequently, the obtained pelletized surfactant-containing molded article has a particulate form as a grinding aid.

4.2% of the A-type zeolite (average particle diameter: 180 mu m) was added thereto, placed in three stages in series under cold air (10 DEG C, 15 m / s), and then ground using FITZMILL (DKA-3, manufactured by Hosokawa Micron Corporation). Screen hole diameter: 1 stage / 2 stages / 3 stages = 8 mm / 6 mm / 3 mm, rpm: shear 3760 rpm). Finally, in a horizontal cylindrical electric mixer (mixer having a cylinder diameter of 585 mm, a cylinder length of 490 mm, a clearance of 20 mm with the inner wall on the inner wall of the drum of the container 131.7L, and two baffles of 45 mm in height), a filling rate of 30% by volume 20% of iron A-type zeolite was added at a rotational speed of 22 rpm and 25 ° C., followed by electric modification for 2 minutes, and the fragrance was sprayed.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle group A, surfactant-containing particle group J (average particle diameter 560micrometer, volume density 0.80g / mL) )

Method for producing surfactant-containing particle group K

Among the compositions shown in Table 13, powder raw materials such as sodium carbonate and A-type zeolite except for post-addition, STPP, and the like were added to a mixer, and then a stirring blade and a chopper were started, followed by an acid precursor of a fluorescent brightener and an anionic surfactant. The mixed liquid with (LAS-H) was added to the mixer (Lodige FKM50D) for about 6 to 7 minutes, and a polymerization reaction was carried out (spindle rotation speed: 150 rpm (Fr number: 2.24), chopper rotation speed: 2880 rpm). . In addition, the jacket of the mixer was poured with cooling water to control the temperature of the neutralized and granulated material (jacket temperature 12 ° C., neutralized and granulated temperature 56 ° C.) to produce particles, and finally, 2% equivalent of a type A zeolite was added to the mixture for 30 seconds. The mixture was stirred during the surface modification and the perfume was sprayed to obtain surfactant-containing particles.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle | grain group A, surfactant-containing particle group K (average particle diameter 380 micrometers, volume density 0.80 g / mL) )

Method for producing surfactant-containing particle group L

Fukae Kogyo Co., Ltd. FS-1200 high speed mixer / granulator was used, and a high volume density powder detergent having the composition shown in Table 13 was prepared in 750 kg units according to the following operation.

A portion of zeolite A, sodium carbonate, sodium sulfate, CMC-Na, layered silicate, acrylic acid / maleic acid copolymer sodium salt, fluorescent brightener, and soap by a mixer, dry blended for 60 seconds at a stirrer speed of 100 rpm and shearing speed of 2000 rpm It was. Water (equivalent to 0.375%) was added and the mixer was allowed to run for 90 seconds at the same stirrer speed and shear rate. LAS-H was added for 300 seconds while the mixer was running at stirrer speed 80 rpm and shear rate 2000 rpm. The temperature was kept at 50 degrees C or less with the jacket passed through. At the completion of neutralization, water (equivalent to 1.4%) and nonionic surfactant as binders were added to the mixer and granulated for 180 seconds at stirrer speed 100 rpm and shearer speed 2000 rpm. The temperature was kept below 50 ° C. by means of a cooling jacket through the water. The product obtained in this step was a granular solid.

The shearing machine of the mixer was stopped, and the stirrer was stirred at a speed of 90 rpm for 120 seconds to add 11% equivalent of a zeolite of A type and surface-modified to spray perfume to obtain surfactant-containing particles.

In order to color a part of obtained surfactant containing particle | grains, 20% aqueous dispersions of pigment | dye are sprayed by the method similar to surfactant containing particle | grain group A, surfactant-containing particle group L (average particle diameter 370 micrometers, volume density 0.85 g / mL) )

Preparation of Bleach Activator Granules

Method for producing a bleaching activator granules E

The bleach activator granule E was prepared in the same manner as the bleach activator granule B, except that the compound represented by the following formula was used as the bleach activator.

Preparation method of bleaching activator granules F

The bleach activator granule E was prepared in the same manner as the bleach activator granule B, except that the compound represented by the following formula was used as the bleach activator.

(Surfactants)

Α-SF-Na: Sodium salt of α-sulfonic acid fatty acid methyl ester having 14 carbon atoms: 16 carbon atoms: 18:82 (manufactured by Lion Corporation, AI = 70%; remainder unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate) , Hydrogen peroxide, water, etc.)

Α-SF-H: α-sulfonic acid fatty acid alkyl ester (methyl ester (paste M-14, pastel M-16 (2: 8 mixture of Lion Oleochemical Co., Ltd.)) was prepared in Japanese Patent Application Laid-Open No. 2001-64248 Sulfonation according to the method disclosed in Example 1, followed by extraction after esterification to produce α-sulfonic acid fatty acid alkyl ester). The compounding quantity of Table 13 shows the weight% as (alpha) -SF-Na neutralized with sodium carbonate at the time of preparation of surfactant containing particle | grains.

LAS-K: straight chain alkyl (10-14 carbon atoms) benzenesulfonic acid (Lion Corporation, LYPON LH-200 (LAS-H, pure content 96%) is neutralized with 48% aqueous potassium hydroxide solution in preparation of surfactant composition) . The compounding quantity of Table 12 shows the weight% as LAS-K.

LAS-Na: straight chain alkyl (10-14 carbon atoms) benzenesulfonic acid (LYPON LH-200 manufactured by Lion Corporation (LAS-H, pure content 96%) is neutralized with 48% aqueous sodium hydroxide solution in preparation of surfactant composition). The compounding quantity of Table 12 shows the weight% as LAS-Na.

LAS-H: linear alkyl (10-14 carbon atoms) benzenesulfonic acid (LYPON LH-200 manufactured by Lion Corporation (96% of LAS-H pure content)) As a compounding quantity in Table 13, it was neutralized with sodium carbonate at the time of preparation of surfactant containing particle | grains. The weight percentage as LAS-Na is shown.

● AOS-K: α-olefinsulfonic acid potassium salt having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation).

AOS-Na: Sodium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation).

Soap: Sodium C12-18 fatty acid (Lion Corporation, Pure content: 67%, Titter: 40-45 ° C., Fatty acid composition: C12: 11.7%, C 14: 0.4%, C16: 29.2%, C18FO Acid): 0.7%, C18Fl (oleic acid): 56.8%, C18F2 (linolinic acid): 1.2%, molecular weight: 289)

AS-Na: sodium alkyl sulfate having an alkyl group having 10 to 18 carbon atoms (SANDET LNM, manufactured by Sanyou Chemical Industries Limited).

Nonionic surfactant 1: by-product of average mole of ethylene oxide and 15 moles of ethylene oxide and ECOROL 26 (alcohols having 12 to 16 carbon atoms, manufactured by ECOGREEN)

Nonionic surfactant 2: adduct of an average of 6 moles of ethylene oxide and ECOROL 26 (alcohol having 12 to 16 carbon atoms, produced by ECOGREEN)

Nonionic surfactant 3: 15 moles of ethylene oxide on average and adduct of pastel M-181 (methyl oleate, manufactured by Lion Oleochemical Company)

PEG6000: Polyethylene glycol manufactured by Lion Corporation, trade name PEG # 6000M (average molecular weight 7300 to 9300)

Cationic surfactant: Praepagen HY (C ₁₂ / C ₁₄ -alkyl dihydroxyethyl methyl ammonium chloride, manufactured by Clariant Japan)

(Fluorescent brightener)

● Fluorescent whitening agent A: CHINOPEARL CBS-Ⅹ (made by Ciba Specialty Chemicals)

● Fluorescent brightener B: CHINOPEARL AMS-GX (made by Ciba Specialty Chemicals)

(Builder)

● No. 1 sodium silicate: JIS No. 1 sodium silicate (manufactured by Nippon Chemical Industries, Ltd.)

● Sodium Sulfate: Neutral Sodium Sulfate (manufactured by Shikoku Corporation)

Sodium chloride: heated salt C of NISSEI (manufactured by Nippon Seien Co., Ltd.).

Sodium Carbonate: Heavy sodium carbonate (soda ash, manufactured by Asahi Glass Co., Ltd.)

Potassium carbonate: Potassium carbonate (made by Asahi Glass Co., Ltd.)

● STPP: Sodium Tripolyphosphate

 Zeolite A: Zeolite A (manufactured by Mizuwa Industrial Chemicals Limited)

Zeolite B: P-type zeolite (DOUCIL A24, manufactured by Crossfield Company)

Layered silicate: crystalline sodium silicate (SKS-6, manufactured by Clariant Japan)

Polymer A: acrylic acid / maleic acid copolymer sodium salt (trade name: Socalan CP7, manufactured by BASF AG)

Polymer B: Sodium Polyacrylate (trade name: Socalan PA30, manufactured by BASF AG)

● PAHIDS: Sodium hydroxyiminosuccinate

ASDA: Aspartic acid and tetrasodium diacetate (Crewat B-ADS / ASDA-4Na, manufactured by Mitsubishi Rayon Co., Ltd.)

● MGDA: methylglycine diacetate trisodium (Trilon, manufactured by BASF AG)

Sodium citrate: Purified sodium citrate L (manufactured by Fuso Chemical Co., Ltd.)

(Spices)

Fragrance A: Fragrance composition A shown in Unexamined-Japanese-Patent No. 2002-146399 [Table 11]-[Table 18].

Fragrance B: Fragrance composition B shown in Unexamined-Japanese-Patent No. 2002-146399 [Table 11]-[Table 18].

Fragrance C: Fragrance composition C shown in Unexamined-Japanese-Patent No. 2002-146399 [Table 11]-[Table 18].

Fragrance D: Fragrance composition D shown in Unexamined-Japanese-Patent No. 2002-146399 [Table 11]-[Table 18].

(Color)

● Pigment A: Ultramarine Blue Pigment (Ultramarine Blue, Dainishelka Color & Chemicals Mfg. Company Limited)

Pigment B: Pigment Green 7 (manufactured by Dainishelka Color & Chemicals Mfg. Company Limited)

Dye C: About 1% of C in the polymer resin dispersion liquid of the spherical resin particle of average particle diameter 0.35 micrometer obtained by radical emulsion polymerization in water dispersion system using acrylonitrile / styrene / acrylic acid as a composition monomer. .I. Pink fluorescent pigment aqueous dispersion obtained after addition of BASIC RED-1 and heat treatment.

(Percarbonate)

● Percarbonate: Sodium percarbonate coated with silicic acid and sodium borate (trade name: SPC-D, manufactured by Mitsubishi Gas Chemical Co., Inc., 13.2% effective oxygen content, average particle diameter 760 µm)

(Bleach activator granules)

● Bleach activator granule A: Tetraacetylethylenediamine granule (brand name Peractive AN, made in Clariant Japan)

Bleach activator granule B: Bleach activator granules obtained by the method for producing bleach activator granule B described above.

Bleach activator granules C: Bleach activator granules obtained by the method for producing bleach activator granules C described above.

Bleach activator granules D: Bleach activator granules obtained by the method for producing the bleach activator granules D described above.

Bleach activator granules E: Bleach activator granules obtained by the method for producing the bleach activator granules E described above.

Bleach activator granules F: Bleach activator granules obtained by the method for producing the bleach activator granules F described above.

(Amorphous Silicate)

Amorphous Silicate A: Britesil H24 (manufactured by PQ Corporation)

Amorphous Silicate B: Britesil C24 (manufactured by PQ Corporation)

Amorphous Silicate C: Britesil H20 (manufactured by PQ Corporation)

Amorphous Silicate D: Britesil C20 (manufactured by PQ Corporation)

Amorphous silicate E: complex of sodium carbonate and amorphous alkali metal silicate, NAB ION 15 (made by Rhodia Company)

(enzyme)

Enzyme A: Everlase 8T (Novozymes A / S) / LIPEX 50T (Novozymes A / S) / Termamil 60T (Novozymes A / S) / Cellzyme 0.7T (Novozymes A / S) = 5: 2: 1 Mixture of 2: 2 (weight ratios)

Enzyme B: Kannase 12T (Novozymes A / S) / LIPEX 50T (Novozymes A / S) / Termamil 60T (Novozymes A / S) / Cellzyme 0.7T (Novozymes A / S) = 5: 2: 1 : 2 (weight ratio)

(Other ingredients)

Bentonite: Laundrosil PR414 (manufactured by SUD-CHEMI Company)

4-methoxyphenol: Kawaguchi Chemical Industries, Ltd. (trade name: MQ-F)

● BHT: Di-t-butylhydroxytoluene, Nikki Universal Company Limited (brand name: BHT-C)

● Sodium tetraborate: Sodium tetraborate, pentahydrate (brand name: Neobor, Borax company make)

● HEDP-4Na: 4-sodium 1-hydroxyethane-1,1-diphosphonic acid (trade name: DAYQUEST 2016D, manufactured by Solutia Japan Limited)

● EDTMP: Ethylenediaminetetra (methylenephosphonic acid) sodium (brand name: BRIQUEST (registered trademark) 422, manufactured by ALBRIGHT & WILSON company)

Montmorillonite: Montmorillonite (ROUNDROSIL powder, manufactured by SUN-CHEMI Company)

● White carbon: fine powder of silica (TOKUSEAL N, Tokyuyama Corporation)

● CMC-Na: Same as Powder 4 in Table 4

(powder)

Powders 1 to 4 are shown in Table 4.

(Bleaching activation catalyst)

Catalysts 1 to 5 are as described above.

(Bleach activator)

Bleach activators 1 to 4 are as described above.

Claims (18)

(a) peroxides dissolved in water to produce hydrogen peroxide, (b) water insoluble or poorly soluble fiber powder selected from the group consisting of powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, and (c) (c-1) bleach activating catalyst and / or (c-2) bleach activating agent Bleach composition, characterized in that it contains. (a) peroxides dissolved in water to produce hydrogen peroxide, (b) a water-insoluble or poorly water-soluble fiber powder selected from the group consisting of powdered cellulose, silk powder, wool powder, nylon powder and polyurethane powder, (c) (c-1) a bleach activating catalyst or (c-1) a bleaching activating catalyst and (c-2) a bleach activating agent, and (d) surfactants Bleaching detergent composition characterized in that it contains. The bleaching detergent composition according to claim 2, wherein the content of the component (d) is 10 to 50% by weight. The composition according to any one of claims 1 to 3, wherein the component (a) is sodium percarbonate. The composition according to claim 4, wherein the component (a) is coated sodium percarbonate. The composition according to any one of claims 1 to 5, wherein the component (b) is powdered cellulose. The composition according to any one of claims 1 to 6, wherein the composition contains the component (c-1), and the bleaching activating catalyst of the component (c-1) comprises manganese. 8. The composition of claim 7, wherein the bleaching activating catalyst of component (c-1) is (tris (salicylideneiminoethyl) amine) -manganese complex. The composition according to any one of claims 1 to 8, wherein the composition (c-1) is contained in an amount of 0.001 to 1% by weight. The bleaching activator of the component (c-2), wherein the bleaching activator of the component (c-2) is 4-decanoyloxybenzoic acid or 4-nonanoyloxybenzenesulfonic acid sodium salt. A composition, characterized in that. The bleaching activating catalyst of the component (c-1) containing (c-1) and (c-2), and (tris (salicylideneiminoethyl) according to any of claims 1 to 9 Amine) -manganese complex, and the bleaching activator of component (c-2) is 4-decanoyloxybenzoic acid or 4-nonanoyloxybenzenesulfonate sodium. The composition according to any one of claims 1 to 11, which contains granules or moldings comprising component (b) and component (c). 13. A composition according to claim 12, wherein the composition contains a binder compound in granules or moldings. The composition according to claim 13, wherein the binder compound is polyethylene glycol having an average molecular weight of 2600 to 9300. The composition according to any one of claims 12 to 14, comprising a surfactant in the granules or moldings. The composition according to any one of claims 12 to 15, wherein the content of component (b) is from 3 to 50% by weight in the granules or moldings. The bleach composition according to any one of claims 12 to 16, wherein the content of component (b) is 0.05 to 3% by weight in the composition. The bleaching detergent composition according to any one of claims 12 to 16, wherein the content of component (b) is 0.005 to 1% by weight of the composition.