JP2010168534A - Bleaching composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bleaching composition which can prevent discoloration and generation of odor and excels in bleaching effect. <P>SOLUTION: The bleaching composition includes: a component (A) of, for example, a coated catalyst prepared by coating a catalyst containing a mixture of a chelate compound selected from amino carboxylic acid represented by formula (I) or the like and at least one of copper compounds and manganese compounds and/or their reactant, with a water insoluble inorganic powder; a component (B) of a surfactant; and a component (C) of a peroxide. The water insoluble inorganic powder is preferably A type zeolite. (In the formula, Z<SP>1</SP>-Z<SP>4</SP>are each independent COOX<SP>1</SP>, a 1-30C alkyl group, a sulfo group or an amino group; at least one of Z<SP>1</SP>-Z<SP>4</SP>is COOX<SP>1</SP>; X<SP>1</SP>is each independently a hydrogen atom, an alkali metal atom or an alkali earth metal atom; R is a hydrogen atom or a hydroxyl group; Q is a hydrogen atom or an alkyl group; and n1 is an integer of 0 or 1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a bleaching composition.

  Conventionally, washing using a detergent composition and a bleaching composition is generally performed on clothing and the like. Some of the bactericidal / sterilizing effects and bleaching effects of the compositions used for these applications are exhibited by oxidation reactions. The oxidation reaction component responsible for such an oxidation reaction is hydrogen peroxide, an inorganic peroxide that liberates hydrogen peroxide in an aqueous solution, a hydrogen peroxide-based compound, and sodium hypochlorite depending on the application. The chlorine-based compounds are used. Recently, hydrogen peroxide-based compounds such as hydrogen peroxide have attracted attention because they can be used easily.

  In such a composition, the performance under low temperature conditions, for example, may be insufficient with only the oxidation reaction component. Thus, for example, a bleaching composition using an oxidation reaction component and an organic peracid precursor having a property of promoting the oxidation reaction has been proposed (for example, Patent Document 1). Also, for example, for the purpose of further improving the detergency and bleaching power of the bleaching composition, a powder bleach composition (for example, a combination of a transition metal such as copper and dipicolinic acid bonded with an oxidation reaction component) Patent Literature 2) and a powder bleaching composition in which a transition metal such as copper, an aminocarboxylic acid, and an oxidation reaction component are used in combination have been proposed (for example, Patent Literature 3).

JP 7-33295 A JP 2008-1736 A JP 2008-104920 A

However, for example, when a chelate substance having an N atom such as aminocarboxylic acid and a transition metal are blended in a bleaching composition as in the above-described technique, an amine-like odor is generated during storage. there were. In addition, when the transition metal is independently added to the bleaching composition, inconveniences such as discoloration of articles to be cleaned such as clothing are likely to occur.
Accordingly, the present invention is directed to a bleaching composition that can prevent discoloration of an object to be cleaned and generation of a strange odor during storage and has an excellent bleaching effect.

  The bleaching composition of the present invention comprises (A) component: a mixture of a chelate compound selected from aminocarboxylic acids represented by the following general formulas (I) and (II), and at least one of a copper compound and a manganese compound; And / or a coated catalyst body in which a catalyst body containing a reactant is coated with a water-insoluble inorganic powder, (B) component: surfactant, and (C) component: peroxide.

(In Formula (I), Z ^{1 to} Z ⁴ each independently represent COOX ¹ , an alkyl group having 1 to 30 carbon atoms, a sulfo group, or an amino group, and at least one of Z ^{1 to} Z ⁴ is COOX ¹ . X ¹ independently represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom, R represents a hydrogen atom or a hydroxyl group, Q represents a hydrogen atom or an alkyl group, and n ₁ represents , Represents an integer of 0 or 1.)

(In Formula (II), Y represents an alkyl group, a carboxyl group, a sulfo group, an amino group, a hydroxyl group, or a hydrogen atom. Z ^{5 to} Z ⁷ are each independently, COOX ² , a hydrogen atom having 1 to 30 carbon atoms, and hydrogen. Represents an alkyl group, a sulfo group, or an amino group in which a part of the atoms may be substituted, and at least one of Z ^{5 to} Z ⁷ is COOX ^2. X ² is independently a hydrogen atom or an alkali metal And represents an atom, an alkaline earth metal atom, or a cationic ammonium group, and n ₂ represents an integer of 0 to 5.)

  The water-insoluble inorganic powder is preferably A-type zeolite.

  According to the bleaching composition of the present invention, it is possible to prevent discoloration of an object to be cleaned and generation of a strange odor during storage, and an excellent bleaching effect.

(Bleachable composition)
The bleaching composition of the present invention comprises (A) component: a chelate compound selected from the aminocarboxylic acids represented by the general formulas (I) and (II) (hereinafter sometimes referred to as component (a)), A catalyst body containing a mixture and / or a reaction product with a copper compound and / or a manganese compound (hereinafter also referred to as component (b)) is a water-insoluble inorganic powder (hereinafter also referred to as component (c)). It contains a coated catalyst body, a component (B): a surfactant, and a component (C): a peroxide.
The bleaching composition includes a detergent composition and a bleaching composition. The bleaching composition is a composition mainly for the purpose of bleaching the object to be cleaned and emphasizing the bleaching power, and the detergent composition is mainly for the purpose of cleaning the object to be cleaned, rather than the bleaching composition. Although the bleaching power is inferior, the composition emphasizes detergency.

<(A) component: Coated catalyst body>
Component (A), which is a coated catalyst body, covers a catalyst body (hereinafter, simply referred to as a catalyst body) containing a mixture and / or reactant of component (a) and component (b) with component (c). It is a thing. In the present invention, the “coating” includes not only a state where the entire surface of the catalyst body is completely covered but also a state where 60% or more of the surface of the catalyst body is covered.

  Although content of (A) component in a bleaching composition is not specifically limited, For example, 0.1-3 mass% is preferable if it is a bleaching agent composition. If it is a detergent composition, 0.1-3 mass% is preferable, and, as for content of (A) component, More preferably, it is 0.5-3 mass%. If the above upper limit is exceeded, the bleaching effect may not be enhanced, and at the same time, damage to clothing may occur, the balance with other ingredients may not be balanced, and the cleaning effect may be insufficient, and the bleaching composition may be stored. Stability and appearance maintenance may be insufficient. This is because if the amount is less than the above lower limit, the bleaching effect may not be improved.

<< (a) Component: Chelate Compound Selected from Aminocarboxylic Acids Represented by General Formulas (I) and (II) >>
The component (a) includes an aminocarboxylic acid represented by the following general formula (I) (hereinafter sometimes referred to as compound (I)) and an aminocarboxylic acid represented by the following general formula (II) (hereinafter referred to as compound). (II) is a selected chelate compound.

(In Formula (I), Z ^{1 to} Z ⁴ each independently represent COOX ¹ , an alkyl group having 1 to 30 carbon atoms, a sulfo group, or an amino group, and at least one of Z ^{1 to} Z ⁴ is COOX ¹ . X ¹ independently represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom, R represents a hydrogen atom or a hydroxyl group, Q represents a hydrogen atom or an alkyl group, and n ₁ represents , Represents an integer of 0 or 1.)

(In Formula (II), Y represents an alkyl group, a carboxyl group, a sulfo group, an amino group, a hydroxyl group, or a hydrogen atom. Z ^{5 to} Z ⁷ are each independently, COOX ² , a hydrogen atom having 1 to 30 carbon atoms, and hydrogen. Represents an alkyl group, a sulfo group, or an amino group in which a part of the atoms may be substituted, and at least one of Z ^{5 to} Z ⁷ is COOX ^2. X ² is independently a hydrogen atom or an alkali metal And represents an atom, an alkaline earth metal atom, or a cationic ammonium group, and n ₂ represents an integer of 0 to 5.)

  Examples of compound (I) include iminodisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, and salts thereof. Examples of compound (II) include nitrilotriacetic acid, methylglycine diacetate, dicarboxymethylglutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetate, or salts thereof. Among these, 3-hydroxy-2,2'-iminodisuccinic acid, methylglycine diacetate, and iminodisuccinic acid are particularly preferable, and the most preferable compound is methylglycine diacetate.

  Examples of the salt include alkali metal salts such as sodium salt and potassium salt, alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt or potassium salt is particularly preferable.

When Z ^{1 to} Z ⁴ in the general formula (I) are COOX ¹ , each X ¹ independently represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. Examples of the alkali metal atom include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium.
When Z ^{1 to} Z ⁴ are COOX ¹ and any ^one of X ¹ is an alkaline earth metal atom, for example, when Z ¹ is COOX ¹ and X ¹ is calcium (Ca), the formula (I ^{Z 1} in) is "-COOCa _1/2". Among these, when Z ^{1 to} Z ⁴ are COOX ¹ , it is preferable that all of X ¹ are sodium or potassium. When Z ^{1 to} Z ⁴ are COOX ¹ , X ¹ may be the same as or different from each other.

At least one of Z ^{1 to} Z ⁴ is COOX ¹ . If any of Z ^{1 to} Z ⁴ is COOX ¹ , then the compound of the present invention is dissolved in water at the time of washing, so that this compound (I) becomes -COO- by ionizing -COOX ¹ respectively. Generates anions. And the -COO- portion of the anion can form a complex with the copper ion or manganese ion released from the component (b).

R represents a hydrogen atom or a hydroxyl group, and is preferably a hydroxyl group.
Q represents a hydrogen atom or an alkyl group. Q is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
n ₁ represents an integer of 0 or 1, and is preferably 1.

Specific examples of the compound (I) include compounds represented by the following chemical formulas (1) to (4). In addition, in these chemical formulas (1) to (4), as a typical example, a case where X ¹ is all hydrogen (H) is shown, but the compound (I) is limited to these structures. It can be selected according to the purpose.

Further, ^Z 1 to Z ⁴ in the compound (I) is an alkyl group may be substituted structures sulfo group _(SO 3 H) or an amino group (NH ₂₎ or the like. The alkyl group may be an alkyl group further having a substituent, and may be linear or branched. Preferably carbon number of an alkyl group is 1-30, More preferably, it is 1-18. In the alkyl group, part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group, an amino group, a hydroxyl group (OH), and a nitro group (NO ₂ ).
From the viewpoint of stabilizing the coordination and improving the bleaching / washing effect, when Z ^{1 to} Z ⁴ are COOX ¹ , it is most preferable that Z ^{1 to} Z ⁴ are carboxyl groups (COOH).

In the general formula (II), Y represents an alkyl group, a carboxyl group, a sulfo group, an amino group, a hydroxyl group, or a hydrogen atom, and a hydrogen atom is preferable.
When Z ^{5 to} Z ⁷ in the general formula (II) are COOX ² , each X ² is independently selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. Represents one kind. Examples of the alkali metal atom include sodium and potassium. Examples of alkaline earth metal atoms include calcium and magnesium.
When Z ^{5 to} Z ⁷ are COOX ² and any one of X ² is an alkaline earth metal atom, for example, when Z ⁵ is COOX ² and X ² is calcium (Ca), the formula (II Z ⁵ in the parentheses) becomes “—COOCa _1/2 ”. Among the above, when Z ^{5 to} Z ⁷ are COOX ² , it is preferable that all of X ² are sodium or potassium. When Z ^{5 to} Z ⁷ are COOX ² , X ² may be the same as or different from each other.

At least one of Z ^{5 to} Z ⁷ is COOX ² . If any of Z ^{5 to} Z ⁷ is COOX ² , by dissolving the catalyst body of the present invention in water at the time of washing, this compound (II) becomes -COO- by ionizing -COOX ² respectively. Generates anions. And the -COO- part of this anion can form a complex with the copper ion or manganese ion released from the component (b).

n ₂ represents an integer of 0 to 5, preferably from 0 to 2, more preferably 1.

Specific examples of the compound (II) include compounds represented by the following chemical formulas (5) to (17). In these chemical formulas (5) to (17), as representative examples, when Z ^{5 to} Z ⁷ are COOX ² , X ² is all hydrogen (H). Compound (II) is not limited to these structures, and can be appropriately selected according to the purpose.

Further, Z ⁵ to Z ⁷ is an alkyl group in the compound (II), may have a structure which is substituted with a sulfo group, or an amino group.
The alkyl group may be an alkyl group further having a substituent, and may be linear or branched. Preferably carbon number of an alkyl group is 1-30, More preferably, it is 1-18. In the alkyl group, part of the hydrogen atoms may be substituted with a substituent. Examples of this substituent include a sulfo group, an amino group, a hydroxyl group, and a nitro group. Z ^{5 to} Z ⁷ are most preferably a carboxyl group (COOH) from the viewpoint of stable coordination and improved bleaching and washing effects.

  In addition to the above compound, as the component (a) constituting the present invention, a compound represented by the following chemical formula (18) can be used.

(A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.
Although content in the bleaching composition of (a) component is not specifically limited, 0.001-2 mass% is preferable, More preferably, it is 0.02-2 mass%, More preferably, it is 0.1-2 mass%. It is. Even if the above upper limit is exceeded, bleaching / cleaning effects may not be enhanced against stain stains on clothes and yellowing stains on clothes that have been worn for a long time. In some cases, clothing damage such as scarlet color cannot be suppressed.

  Thus, by mix | blending (a) component, the clothes which are to-be-washed | cleaned objects by forming a complex with the below-mentioned (b) component at the time of washing or a bleaching process, for example, and being used with (C) component The bleaching / cleaning effect can be exhibited.

<< (b) component: copper compound and / or manganese compound >>
The component (b) is at least one of a copper compound and a manganese compound, that is, a copper compound and / or a manganese compound. The component (b) is not particularly limited as long as it is soluble in water and releases copper or manganese ions at that time. Examples of water-soluble copper or manganese compounds include inorganic salt compounds such as nitrates, sulfates, chlorides, perchlorates, ammonium chlorides, cyanides, acetates, acetylacetonates, gluconates, Organic compounds such as oxalate and tartrate are listed. Among these, copper sulfate or manganese chloride is preferable in terms of price and usability. From the standpoint of maintaining product performance and bleaching / washing performance, copper compounds are preferred, and copper sulfate is more preferred.
These can be used individually by 1 type or in combination of 2 or more types.

The amount of component (a) to component (b) is 1 molar equivalent or more, preferably 1 to 20 molar equivalents, and more preferably 5 to 20 molar equivalents. The component (a) in excess of the component (b) is preferable from the viewpoint of the stability of the component (A), but is preferably 20 molar equivalents or less from the viewpoint of the bleaching effect.
The component (b) may be used for forming the catalyst body of the component (A) after forming a complex with the component (a), or may be blended with the component (A) without being complexed.

<< (c) component: water-insoluble inorganic powder >>
The component (c) is a water-insoluble inorganic powder. The component (c) is not particularly limited as long as it is a water-insoluble inorganic powder, but aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous zeolite), calcium silicate, aluminum oxide, Aluminum hydroxide, talc (hydrous magnesium silicate), bentonite, alumina (porous alumina), titanium oxide, zinc oxide, apatite (phosphate mineral), diatomaceous earth, glass (porous glass), oxide materials: nanoporous crystals, Examples thereof include lanthanum strontium manganite, porous duopside, carbon, silicon carbide, titanium carbide, and silicon nitride. Among these, titanium oxide, talc, and aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, and amorphous zeolite) are preferable, and A-type zeolite is particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.

  The particle diameter of the component (c) is preferably 10 μm or less, more preferably 5 μm or less, considering the coating efficiency due to interparticle forces such as van der Waals force. This is because the component (c) can sufficiently cover the surface of the catalyst body with interparticle forces such as van der Waals force if the particle diameter is as described above. Here, the average particle size and the particle size distribution are values measured by a laser light scattering method (for example, a particle size distribution measuring device (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.)). Is the volume-based median diameter.

  Among the above-mentioned component (c), for example, zeolite includes Tokusil Fine Seal (trade name) manufactured by Tokuyama Co., Ltd., Zeolite manufactured by Shanxi Yuchi ChangliHigh-Tech Co., Ltd. (Trade name), 4A ZEOLITE (trade name) manufactured by ALUMINUM CORPORATION OF CHINA., LTD., 4A Zeolite (trade name) manufactured by Huying Chemical Products Co., Ltd. ), Zeolite 4A Type (trade name) manufactured by Thai Silicate Chemicals Co., Ltd., COSMO FINE CHEMICALS COLITE-P (trade name) manufactured by CO., LTD.), VALFOR 100 Zeolite NaA manufactured by PQ Chemical (PQ Chemicals Limited), and the like.

  The content of the component (c) in the component (A) is preferably catalyst body / (c) component (mass ratio) = 70/2 to 70/30, more preferably 70/9 to 70/30. If it is within the above-mentioned range, it is possible to prevent the generation of a strange odor and suppress clothing damage such as discoloration, and even if the component (c) exceeds the above upper limit, the effect may not be enhanced. .

≪Optional components in the catalyst body≫
If necessary, a binder compound, a surfactant, sodium sulfate, an inorganic substance of sodium carbonate, an organic acid salt such as sodium citrate, a film-forming polymer, or the like may be added to the catalyst body.

[Binder compound]
The binder compound can be added as necessary when granulating or molding the catalyst body. The binder compound is not particularly limited as long as it is a binder compound. For example, various nonionic surfactants, saturated fatty acids having 12 to 20 carbon atoms, polyethylene glycol having an average molecular weight of 500 to 25,000, and polycarboxylic acid type having an average molecular weight of 1,000 to 1,000,000. Examples thereof include a polymer and a salt thereof (polyacrylic acid, a copolymer of polyacrylic acid and maleic acid, and the like). Among them, polyethylene glycol having an average molecular weight of 2500 to 10,000, a block polymer of ethylene oxide and propylene oxide (hereinafter referred to as binder compound-1), and a nonionic surfactant having an HLB value of 16 or more (hereinafter referred to as binder compound-2). One or more binder compounds selected from are preferred. Examples of the binder compound-2 include polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil.

  Furthermore, as the binder compound-1, polyethylene glycol having an average molecular weight of 7300 to 9300 or a block polymer of ethylene oxide and propylene oxide is preferable, and as the binder compound-2, an ethylene oxide addition mole containing an alkyl group having 18 or more carbon atoms is used. A nonionic surfactant having a number of 40 to 80 and an HLB value of 16 or more is more preferable. By using such a binder compound, a high detergency can be exhibited by rapidly forming a complex in the cleaning liquid when the bleaching composition is dissolved. Moreover, the effect of suppressing damage to the object to be cleaned can be expected, and the storage stability can be improved.

  In addition, the average molecular weight of the binder compound in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description. The HLB value is an HLB value obtained by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991, page 234).

16-98 mass% is preferable and, as for content of the binder compound in a catalyst body, 20-90 mass% is more preferable. Even if the above upper limit is exceeded, there is a possibility that the peroxide stability and appearance maintenance of the bleaching composition and the effect of suppressing damage to the object to be cleaned are not enhanced. This is because if it is less than the lower limit, the effect of maintaining the appearance of the bleaching composition may be insufficient, or the molding of the catalyst body may be difficult. The content of the binder compound in the bleaching composition is preferably 0.016 to 2.94% by mass, and more preferably 0.25 to 2.7% by mass. Even if the above upper limit is exceeded, the stability and appearance of the peroxide of the bleaching composition may not be enhanced, and the damage suppressing effect on the object to be cleaned may not be enhanced, and it is sufficient that the balance with other components cannot be achieved. May not be able to obtain a good cleaning effect. This is because if it is less than the above lower limit value, the stability of the peroxide and the effect of maintaining the appearance of the bleaching composition may be insufficient, or it may be difficult to mold the catalyst body.
In addition, you may use the binder compound disperse | distributed or melt | dissolved in water or a solvent. By using as such a solution, the solubility of the component (b) in the cleaning liquid can be improved, and a high bleaching / cleaning effect can be efficiently exhibited.

  When the surfactant is blended in the catalyst body, the blending amount of the surfactant may be reduced from the blending amount of the binder compound.

[Surfactant]
In order to improve the solubility in the washing bath (washing water), the catalyst body has a polyoxyalkylene alkyl ether, an olefin sulfonate, an alkylbenzene sulfonate, A surfactant such as alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt or fatty acid methyl ester sulfonate salt, or a mixture thereof may be blended.

  As polyoxyalkylene alkyl ether, the alkyl group preferably has 10 to 14 carbon atoms, more preferably an adduct of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO). The average number of moles added is preferably 4 to 20, more preferably 5 to 15 in terms of the total amount of EO and PO in the case of adding only EO or PO, or mixing EO and PO. The molar ratio of EO / PO is preferably 5/0 to 1/5, more preferably 5/0 to 1/2.

As the olefin sulfonate, sodium or potassium salt of α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms is preferable.
The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms.
As the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as a sodium salt is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable.
As a polyoxyethylene alkyl ether sulfate ester salt, the polyoxyethylene alkyl ether sulfate ester salt which has a C10-C14 alkyl group is preferable, More preferably, it is a sodium salt. Here, the average degree of polymerization of the oxyethylene group (hereinafter, the average degree of polymerization is indicated by POE) is preferably 1 to 10, more preferably 1 to 5. As such polyoxyethylene alkyl ether, polyoxyethylene lauryl ether sulfate sodium (POE = 2 to 5) and polyoxyethylene myristyl ether sulfate sodium (POE = 2 to 5) are more preferable.

  As content in the catalyst body of this surfactant, 0-50 mass% is preferable, More preferably, it is 3-40 mass%, More preferably, it is 5-30 mass%.

  In order to improve the productivity when granulating the catalyst body, an inorganic substance such as sodium sulfate or sodium carbonate, or an organic acid salt such as sodium citrate may be added.

<< (A) Component Production Method >>
(A) As a manufacturing method of a component, the process (molding process) of obtaining the catalyst body containing the mixture of (a) component and (b) component, or the compound of (a) component and (b) component, If it has a process (coating process) of coat | covering a catalyst body with (c) component, it will not specifically limit.

[Molding process]
As the molding step, for example, an optional component including the component (a), the component (b) and the binder compound is mixed with a mixer or a kneader, and then 1 mm through a perforated die or screen using an extrusion molding machine. A method of extruding and crushing to a noodle-like shape can be mentioned. Alternatively, there may be mentioned a method of dissolving and dispersing the components (a), (b) and the binder compound other than the binder compound in the melted binder compound, forming a massive substance in a mixer, and then pulverizing with a pulverizer. Alternatively, using an agitation granulator, a container rotary granulator, or a fluidized bed granulator, etc., the (a) component, the optional component except the component (b) and the binder compound are mixed and further stirred or fluidized. However, a method of granulating by adding a liquid binder compound can be mentioned. Further, for example, after mixing optional components including the component (a), the component (b), and the binder compound, compression molding may be performed with a tableting machine or a brisketting machine to obtain a molded product. Furthermore, if necessary, a method of obtaining a particulate catalyst body by pulverizing the molded product with a pulverizer may be mentioned. By forming a catalyst body by such a molding process, it is possible to prevent the copper compound and / or manganese compound from reacting with peroxides and dyes alone when dissolved while in contact with clothing. It is possible to prevent discoloration due to oxygen generation and changes due to changes in the electronic state of the dye.

  The binder compound used in the molding step is preferably used after being melted in advance, for example, preferably 50 to 100 ° C, more preferably 50 to 90 ° C.

  The size of the catalyst body obtained in the molding step is not particularly limited. For example, when the catalyst body is particulate, the average particle diameter (mass 50%) of the catalyst body is preferably 100 to 1400 μm, 300 -1000 micrometers is more preferable. This is because a good odor control effect and solubility can be obtained within the above range.

In addition, in this specification, an average particle diameter (mass 50%) is a value calculated | required by the method of calculating | requiring a particle size distribution using a sieve as follows, and calculating from the particle size distribution.
First, the measuring object (sample) is classified using a 9-stage sieve and a saucer having openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm. Do. In the classification operation, first, the 9-stage sieve is stacked above the pan so that the openings gradually increase, and a sample of 100 g / time is placed on the top of the sieve having the top opening of 1,680 μm. . Next, it was covered and attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, it remained on each sieve and saucer. Samples are collected for each mesh and the sample mass is measured.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (mass 50%) is obtained from the following formula (i), where c is the total mass frequency from the first to the a μm sieve and c is the mass frequency on the a μm sieve.

  When (a) component, (b) component, and a binder compound are used for manufacture of a catalyst body, each content is (a) component / (b) component / binder compound = 1-80 mass% / 1-4 mass % / 16-98 mass% is preferable, and 5-80 mass% / 1-4 mass% / 16-94 mass% is more preferable. The component (a) is preferably in the above range from the viewpoint of storage stability of the product, appearance, bleaching effect, clothing damage and discoloration, and the component (b) is from the viewpoint of product storage stability, damage to clothing and discoloration. The range is preferable, and the binder compound is preferably in the above range from the viewpoint of storage stability of the product, manufacturability, shape retention, and solubility.

  All or part of the component (a) and the component (b) in the molding step can be replaced with a complex that is a reaction product of the component (a) and the component (b). This is because the molding step using the complex of the component (a) and the component (b) has an excellent balance of production time, complex yield, simplicity, etc., and is advantageous in industrial production. Moreover, the mixture obtained by the below-mentioned collection | recovery process can be used as it is as an oxidation catalyst, without isolate | separating byproduct salt, and does not involve a complicated process. However, when it is necessary to obtain an oxidation catalyst as a higher-purity complex, the reaction solution obtained by the reaction treatment is allowed to stand in a cool and dark place for 1 hour to 1 week, and the resulting precipitate, that is, the solid complex is filtered. You may employ | adopt the collection | recovery method obtained by another.

Although the manufacturing method of the complex of (a) component and (b) component is not specifically limited, For example, a complex can be manufactured with the following method.
First, in the solvent, the component (b) and the component (a) to be a ligand are added and dissolved, and an alkali agent is added as necessary, preferably room temperature to 100 ° C, more preferably 25 ° C. These are stirred at a room temperature to a certain degree (reaction treatment). The reaction treatment time is preferably 1 minute or more, more preferably 1 minute to 5 hours, and more preferably about 10 minutes. Immediately after the completion of the reaction process, the solvent is distilled off from the reaction solution under reduced pressure, and the solid complex and by-product salt produced by the reaction process are recovered in the form of a mixture (recovery process).

The particle size of the resulting complex is not particularly limited, but the average particle size is in the range of 5 to 200 μm, and the particle size distribution is such that the particles having a particle size of 1 to 100 μm are 10% by mass or more of the entire complex. preferable.
Here, the average particle size and the particle size distribution are values measured by a laser light scattering method (for example, a particle size distribution measuring device (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.)). Is the volume-based median diameter.

  If an unreacted ligand remains after reacting the component (b) with the ligand comprising the component (a), it is not always necessary to remove it.

  The solvent used for producing the complex is preferably a polar solvent, preferably capable of dissolving the component (a) at room temperature, and further capable of being distilled off under reduced pressure at 200 ° C. or lower. Specific examples include water, ethanol, methanol, isopropanol, acetonitrile, acetone, dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and the like. One or more of these can be used, but the price, safety, From the viewpoint of easiness of distillation, one or more of water, ethanol and methanol are preferable, and water is particularly preferable.

  As the alkali agent, triethylamine, sodium hydroxide, sodium carbonate and the like can be used. The component (b) used when producing the complex is preferably one that dissolves in a solvent to generate copper or manganese ions. In addition to the various water-soluble metal salts exemplified above, the component (b) can be used as a solvent. Other soluble salts (for example, organic solvent-soluble salts) can also be used. As described above, since water is preferably used as the solvent, a water-soluble metal salt is preferably used as the component (b).

  The complex structure formed here is not particularly limited, and the number of ligands per copper or manganese atom may be one or plural, and the copper and / or manganese atoms constituting one complex may also be one. One or more may be sufficient. That is, the complex may be mononuclear, binuclear, or cluster. Moreover, when it is a polynuclear complex, the transition metal contained therein may be only one kind of copper element, or may be plural kinds, for example, when copper and manganese are mixed. Furthermore, in the case of a polynuclear complex, it may be cross-linked by a cross-linking species such as oxygen, sulfur or halogen atom. Further, as such a complex, when at least one anion generated from the component (a) is coordinated to a copper or manganese atom, other ligands can be used in actual use of the catalyst body. Further, it may be coordinated. Examples of such other ligands include various functional groups and atoms (described below) such as a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxylic acid group, and a thiol group. , Halogen atoms, etc.), solvent water and the like.

  In the catalyst body, when the complex of the component (a) and the component (b) is used together with the binder compound, each content is preferably complex / binder compound = 2 to 84% by mass / 16 to 98% by mass, 84 mass% / 16-94 mass% is still more preferable. The above range is preferable from the viewpoint of storage stability of the bleaching composition, damage to clothing and discoloration.

[Coating process]
The coating step is not particularly limited as long as the catalyst body obtained in the molding step can be coated with the component (c). For example, the component (c) and the catalyst body are combined with a horizontal cylindrical rolling mixer (cylinder diameter). 585mm, cylinder length 490mm, container 131.7L drum inner wall surface with two baffle plates with clearance 20mm and height 45mm with inner wall surface), filling rate 30% by volume, rotation speed 22rpm, 25 ° C It is possible to employ a dry coating that rolls and mixes for 1 minute under certain conditions.
The mixing time in the coating step is preferably 1 minute to 90 minutes, more preferably 1 minute to 60 minutes. The Froude number (Fr) defined by the following formula (ii) indicates the powder mixing property in the horizontal cylindrical rolling mixer. It is preferable to select the condition that the fluid number is 0.011 or more and less than 1, more preferably 0.05 to 0.7, and still more preferably 0.1 to 0.65. When the fluid number is less than 0.011, the catalyst body and the component (c) are not sufficiently wound up, and a uniform coated catalyst body may not be obtained. When the Froude number is 1 or more, centrifugal force is strongly applied to the catalyst body and the component (c), and it is difficult for the catalyst body and component (c) to fall in the mixer. In some cases, the production efficiency of the coated catalyst body is reduced.

Fr = V ² / (R × g) (ii)
[V: peripheral speed (m / s) at the tip of the stirring blade, R: rotational radius (m) of the stirring blade, g gravitational acceleration (m / g ² )]

The volume filling rate of the horizontal cylindrical rolling mixer is preferably 10 to 70% by volume, more preferably 15 to 60% by volume, and still more preferably 20 to 45% by volume.
The relative humidity in the coating step is preferably 50 to 90% RH. The temperature condition in the coating step can be determined according to the melting point of the binder compound used in the molding step. For example, the temperature is preferably 10 ° C. to the melting point of the binder + 10 ° C., more preferably 20 ° C. to the melting point of the binder, more preferably 25. It is the temperature of -5 degreeC of melting | fusing point of a binder-binder.
Here, the melting point in the present invention is a value measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test method” (the same applies hereinafter).

  The degree of coverage (coverage) of the catalyst body with the component (c) is 60% or more of the surface area of the catalyst body, and preferably 90% or more. Generation | occurrence | production of a strange odor can be suppressed because the catalyst body is coat | covered with (c) component. Although the mechanism for suppressing the generation of off-flavor is not clear, it can be presumed that the off-odor generation is suppressed by reducing the contact area between the catalyst body and the other detergent components, and the off-flavor generated without being suppressed is also adsorbed.

  The coverage is confirmed by using, for example, the component (A) using a microscope (manufactured by Asahi Optical Co., Ltd., Handi Scope TM) or a scanning electron microscope (eg, Shimadzu Corporation, SUPERSCAN SS-550). it can. For example, the surface of the component (A) is observed with a microscope or SEM, and the ratio of the image area covered with the component (c) to the image area of the catalyst body in the image is calculated by image processing or the like. The coverage of the medium can be confirmed.

≪ (B) component: surfactant≫
Component (B) is a surfactant. Examples of the component (B) include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and these can be used alone or in combination of two or more.

Examples of anionic surfactants include the following.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(11) C14-18 fatty acid methyl ester sulfonate (MES)

  These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.

  The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used. Examples of nonionic surfactants include the following.

(1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 3 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (III) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.

R ⁹ CO (OA) _q OR ¹⁰ (III)
[Wherein, R ⁹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents an alkylene having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably 2 to 3 carbon atoms. An oxide addition unit is shown, q shows the average addition mole number of alkylene oxide, and is generally 3-30, preferably 5-20. OR ¹⁰ is a lower (1 to 4 carbon) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]

(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

  Among the nonionic surfactants described above, the nonionic surfactant (1) is preferable, and among them, polyoxyethylene having an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 12 to 16 carbon atoms. Alkylene alkyl ethers or polyoxyalkylene alkenyl ethers are particularly preferred.

Further, polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB value of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester obtained by adding ethylene oxide to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used alone or in combination of two or more.

The cationic surfactant is not particularly limited as long as it is conventionally used in detergents, and various cationic surfactants can be used. Examples of the cationic surfactant include the following.
(1) Di long chain alkyl dishort chain alkyl type quaternary ammonium salt (2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt (3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt “Long-chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyoxy having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms An alkylene group is mentioned as a suitable thing.

  The amphoteric surfactants are not particularly limited as long as they are conventionally used in detergents. Examples thereof include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

  In addition, (B) component is not limited to the said surfactant, These can be used combining 1 type (s) or 2 or more types as appropriate.

  In the bleaching composition of the present invention, from the viewpoint of stability, the component (B) is preferably prepared as a surfactant-containing particle as a particle different from the component (A) and the component (C). In particular, it is preferable to prepare the surfactant excluding the surfactant used as the granulating base (C) and the binder compound of the catalyst body as the surfactant particles containing the component (B).

  A method for producing a surfactant-containing particle suitable for use in a bleaching composition comprises a surfactant-containing particle having an anionic surfactant as a main surfactant and a nonionic surfactant as a main surfactant. It can be roughly divided into two types of surfactant-containing particles.

[Surfactant-containing particles containing an anionic surfactant as the main surfactant]
Surfactant-containing particles having an anionic surfactant as a main surfactant (hereinafter referred to as anionic surfactant-containing particles) are those containing an anionic surfactant as an essential component and blended in the anionic surfactant-containing particles. It means the particles having the highest content of anionic surfactant among the existing surfactants. Accordingly, other surfactants such as nonionic surfactants, cationic surfactants, and amphoteric surfactants other than anionic surfactants can be suitably blended although their contents are limited.

  The anionic surfactant used in the anionic surfactant-containing particles is not particularly limited as long as it is conventionally used in detergents, as mentioned above as the component (B). Surfactants can be used. In the anionic surfactant-containing particles, the surfactant can be used alone or in combination of two or more of the anionic surfactants with the anionic surfactant as the main surfactant.

  The content of the total surfactant in the anionic surfactant-containing particles can be determined in consideration of the cleaning performance desired for the bleaching composition. For example, the content is preferably 10 to 90% by mass, more preferably It is 15-70 mass%, More preferably, it is 15-50 mass%. This is because a sufficient cleaning effect can be exhibited within the above range. Moreover, as mass ratio of anionic surfactant / other surfactant, it is 100 / 0-50 / 50, Preferably it is 100 / 0-55 / 45, More preferably, it is 95 / 5-70 / 30.

In the surfactant-containing particles having an anionic surfactant as a main surfactant, the various additives and auxiliary components can be used without any particular limitation.
Among these, examples of the inorganic builder include potassium salts such as potassium carbonate and potassium sulfate having an effect of improving solubility, and alkali metal chlorides such as potassium chloride and sodium chloride. Among them, potassium carbonate, alkali metal chlorides such as potassium chloride and sodium chloride are preferable from the viewpoint of the balance between the effect of improving solubility and cost.

When compounding potassium carbonate, the content thereof is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 5 to 10% by mass in the surfactant-containing particles from the viewpoint of improving the solubility. %.
When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 3 to 3% in the surfactant-containing particles from the viewpoint of improving the solubility. 7% by mass.

  The physical property value of the anionic surfactant-containing particles is not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1.2 g / mL, more preferably 0.6. -1.1 g / mL. The bulk density is a value measured according to JIS-K3362 (the same applies hereinafter).

Moreover, an average particle diameter (mass 50%) becomes like this. Preferably it is 200-1500 micrometers, More preferably, it is 300-1000 micrometers. If the average particle size (mass 50%) is less than 200 μm, dust may be easily generated, while if it exceeds 1500 μm, the solubility may be insufficient. Further, the fluidity of the surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If the angle of repose exceeds 60 °, the handleability of the particles may deteriorate.
The angle of repose can be measured by a so-called angle-of-repose angle of repose measurement method that measures the angle formed by the horizontal surface of the slip surface formed when particles filled in the container flow out.

Surfactant-containing particles having an anionic surfactant as a main surfactant can be largely obtained by the following two methods.
(1) A method of granulating a neutralized salt type anionic surfactant.
(2) A method in which an acid precursor of an anionic surfactant is dry neutralized and granulated.

(1) The method of granulating a neutralized salt type anionic surfactant can be obtained by the following granulation method.
(1-1) An extrusion granulation method in which a raw material powder of a detergent component and a binder compound (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, and then extruded and granulated.
(1-2) Kneading and kneading granulation method of kneading and kneading and then crushing and granulating the obtained solid detergent,
(1-3) Stirring granulation method in which a binder compound is added to the raw material powder and stirred and granulated with a stirring blade,
(1-4) Rolling granulation method in which a binder compound is sprayed and granulated while rolling raw material powder,
(1-5) Fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder.

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

Any suitable acid precursor of the anionic surfactant can be used as long as it is an acid precursor of the anionic surfactant that can be suitably used as described above. Moreover, although it does not specifically limit as alkaline powder as a neutralizing agent, An alkali metal carbonate, an alkali metal silicate, an alkali metal phosphate, etc. are mentioned. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate / potassium, etc., and examples of the alkali metal silicate include sodium silicate, layered sodium silicate, and the like. Examples of the phosphate include sodium tripolyphosphate and sodium pyrophosphate. Among these, alkali metal carbonates are preferable, and sodium carbonate, potassium carbonate, and sodium carbonate / potassium are particularly preferable. These can use 1 type (s) or 2 or more types.
The anion-containing surfactant particles granulated by the above-described method can be classified as necessary, and only the surfactant-containing particles having a desired particle size can be used in products.

(Surfactant-containing particles in which the nonionic surfactant is the main surfactant)
Surfactant-containing particles in which the nonionic surfactant is the main surfactant (hereinafter referred to as non-ionic surfactant particles) contain non-ionic surfactant as an essential component and are incorporated in the non-ionic surfactant particles. It means a particle having the highest content of nonionic surfactant among the surfactant components. Accordingly, other surfactants such as anionic surfactants, cationic surfactants, and amphoteric surfactants other than nonionic surfactants can be blended although their contents are limited.

The nonionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various nonionic surfactants can be used. As the nonionic surfactant, the same nonionic surfactants as those listed above for the component (B) can be used.
Nonionic surfactants in the nonionic surfactant-containing particles include polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or lower and an HLB of 9 to 16, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers, Fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, and fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester are preferred. In addition, other surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and the like as listed in the surfactants of the binder compound used in the catalyst body can be suitably used. is there. The said surfactant can be used 1 type or in combination of 2 or more types suitably, and nonionic surfactant can be used in combination of 1 type, or 2 or more types in nonionic surfactant particle | grains.

  The content of all the surfactants in the nonionic surfactant-containing particles is preferably 5 to 85% by mass, more preferably 10 to 60% by mass in the surfactant-containing particles from the viewpoint of imparting sufficient cleaning performance. It is. Moreover, as mass ratio of 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.

  Examples of other components contained in the nonionic surfactant-containing particles include inorganic and organic cleaning builders. As the cleaning builder, a cleaning builder that can be blended with the anionic surfactant-containing particles described above can be similarly used. The same applies to the content of suitable cleaning builder and cleaning builder.

  The nonionic surfactant particles preferably contain an oil-absorbing carrier for supporting the nonionic surfactant, a clay mineral as a granulating aid, and the like.

  As the oil-absorbing carrier, an oil-absorbing substance having an oil absorption amount represented by the JIS-K5101 test method of preferably 80 mL / 100 g or more, more preferably 150 to 600 mL / 100 g is suitably used. Examples of such an oil-absorbing carrier include components described in JP-A-5-125400 and JP-A-5-209200. These oil-absorbing carriers can be used alone or in combination of two or more. The oil-absorbing carrier is preferably contained in the nonionic surfactant particles in an amount of 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass.

As the clay mineral, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are particularly preferable. The clay mineral that can be 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 0.2. ~ 1.5 g / mL.
Specific examples of such clay minerals include components described in JP-A-9-87691.

  The clay mineral is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 10% in the surfactant-containing particles having a nonionic surfactant as a main surfactant. It is contained by mass.

  As the nonionic surfactant particles used in the present invention, those that can be suitably blended in the various anionic surfactant particles as an auxiliary component can be used.

  The physical property value of the nonionic surfactant-containing particles is not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to 1.2 g / mL, more preferably 0.6. -1.1 g / mL. The average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. When the average particle size is less than 200 μm, dust may be easily generated, while when it exceeds 1500 μm, the solubility may be insufficient. Further, the fluidity of the surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

  The nonionic surfactant-containing particles can be obtained by the same granulation method as that for the anionic surfactant-containing particles.

  When such surfactant-containing particles are used, the bleaching composition of the present invention is prepared by mixing the anionic surfactant-containing surfactant particles and / or nonionic surfactant-containing particles with other components. Can do.

Content of (B) component in a bleaching composition can be determined in consideration of the use etc. of a bleaching composition.
For example, when the bleaching composition is a detergent composition, the content of the component (B) in the detergent composition is preferably 10 to 50% by mass, and 15 to 40% by mass from the viewpoint of imparting sufficient cleaning performance. Is more preferable, and 15-35 mass% is further more preferable. In addition, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more of the total surfactant, more preferably 80% by mass or more, and further preferably 95% by mass or more.
Further, when the bleaching composition is a bleaching composition, from the viewpoint of improving the solubility of the hydrophobic component (fragrance, etc.) in the cleaning liquid and the permeability to the hydrophobic component clothing, the surfactant-containing particles In addition, you may mix | blend (B) component further. For example, the content of the component (B) in the bleaching composition is preferably 0.1 to 15% by mass, and more preferably 0.2 to 10% by mass. Even if the upper limit is exceeded, the bleaching effect may not be enhanced against stain stains on clothing or yellowing stains on clothing that has been worn for a long time, and sufficient surfactant content is ensured if the lower limit is exceeded. In some cases, the cleaning effect is insufficient.

<(C) component: peroxide>
Component (C) is a peroxide that dissolves in water to generate hydrogen peroxide. Examples of the component (C) include sodium percarbonate, sodium perborate, sodium perborate trihydrate and the like. From the viewpoint of solubility during use and storage stability, sodium percarbonate. Is preferably used. Sodium percarbonate is more preferably coated sodium percarbonate to further improve stability during storage. Particularly preferred are those coated with silicic acid and / or silicate and boric acid and / or borate, and those coated with a combination of a surfactant such as LAS and an inorganic compound. Specifically, as described in Japanese Patent No. 2,189,991 and the like, it is coated by spraying silicic acid and / or alkali metal silicate aqueous solution and boric acid and / or alkali metal borate aqueous solution. Or coated with an aromatic hydrocarbon sulfonic acid and / or an alkali silicate alkali salt, carbonate, bicarbonate and sulfate having an average particle size (mass of 50%) such as Japanese Patent No. 2871298. It is preferable to use a material coated with a water-insoluble organic compound such as paraffin or wax, or powder blend with various inorganic materials such as sodium carbonate or sodium hydrogencarbonate for non-hazardous material. Furthermore, when the water content in the bleaching composition is high due to the incorporation of a surfactant, etc., a coated peroxide coated with sodium percarbonate and silicic acid and sodium borate, an aromatic hydrocarbon sulfonic acid and an alkali silicate alkali salt, It is more preferable to use one coated with carbonate, bicarbonate and sulfate. These peroxides can be used alone or in combination of two or more.

  The method for producing coated sodium percarbonate is disclosed in JP-A-59-196399 and USP4526698 (both sodium percarbonate is coated with borate), as well as JP-A-4-31498 and JP-A-6-40709. Further, the methods described in JP-A-7-118033 and Japanese Patent No. 2871298 can also be mentioned. The average particle size of the inorganic peroxide is preferably 200 to 1000 μm, more preferably 500 to 1000 μm. In order to satisfy both solubility and stability, particles having a particle size of less than 125 μm and particles exceeding 1400 μm are (C) It is preferable that it is 10 mass% or less in a component. In the bleaching composition, considering the stability of the peroxide, the water content is preferably 2% by mass or less.

  Although content of (C) component in a bleaching composition is not specifically limited, For example, if it is a detergent composition, 1-30 mass% is preferable, More preferably, 2-20 mass%, More preferably, 2-18 mass %. For example, in the case of a bleaching composition, the content is preferably 30 to 90% by mass, more preferably 30 to 70% by mass. Even if the above upper limit is exceeded, the bleaching effect may not be enhanced against stain stains on clothing or yellowing stains on clothing that has been worn for a long time, and washing is not possible because sufficient surfactant content cannot be secured. The effect may be insufficient. If it is less than the above lower limit value, a sufficient bleaching effect may not be obtained for stubborn stains.

<Optional component of bleaching composition>
In addition to the above components (A) to (C), various additives and the like can be blended in the bleaching composition as necessary in a range that does not adversely affect the effects of the present invention. Specifically, it is shown below.

≪Detergency Builder≫
Other ingredients included in the bleaching composition include inorganic and organic detergency builders.
[Inorganic builder]
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate, alkali metal sulfites such as sodium sulfite and potassium sulfite, and crystalline layered sodium silicate (for example, manufactured by Clariant Japan Co., Ltd.). Product name [Na-SKS-6] (δ-Na 2 O · 2SiO 2)) and other crystalline alkali metal silicates, amorphous alkali metal silicates, sulfates such as sodium sulfate and potassium sulfate, sodium chloride, potassium chloride And alkali metal chlorides such as crystalline aluminosilicate, amorphous aluminosilicate, and the like. Among inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, and aluminosilicate are preferable.

  As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, but crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability. The content of the crystalline aluminosilicate is preferably 1 to 40% by mass of the bleaching composition, and 2 to 30% by mass is particularly preferable in terms of powder physical properties such as detergency and fluidity.

  When mix | blending potassium carbonate, the content is from the point of the effect of a solubility improvement, Preferably it is 1-15 mass% in a bleaching composition, More preferably, it is 2-12 mass%, More preferably, it is 5-5. 12% by mass.

  When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably from the viewpoint of the effect of improving solubility. It is 3-7 mass%.

  When blending the crystalline alkali metal silicate in the bleaching composition, the content is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, still more preferably 3 to 20% by mass, and particularly preferably 5%. It is preferable from the point of a detergency that it contains -15 mass%.

[Organic Builder]
Examples of organic builders include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, And polysaccharide derivatives such as polysaccharide oxides such as cellulose, amylose and pectin.

Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A No. 54-52196) are suitable.
The content of the organic builder is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass in the bleaching composition.

  The detergency builder can be used alone or in combination of two or more. For the purpose of improving the detergency and soil dispersibility in the cleaning liquid, it is preferable to use an organic builder such as polyacrylate and acrylic acid-maleic acid copolymer salt together with an inorganic builder such as zeolite. The content of the detergency builder is preferably 10 to 80% by mass, more preferably 20 to 75% by mass in the bleaching composition in order to impart sufficient detergency.

≪Bleach activator≫
The bleach activator is an organic peracid precursor and is a compound that generates an organic peracid by a peroxide such as hydrogen peroxide. Specific examples of the bleach activator include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, undecanoyloxybenzenesulfone. Sodium acid, sodium dodecanoyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, Examples include decanoyloxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene, and the like. Moreover, the compound represented by the following general formula (IV) and (V) is mentioned.

[Wherein, R ¹ is an alkyl group having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3 carbon atoms which may be separated by an ester group, an amide group or an ether group, and R ⁶ is an ester. It is an alkylene group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms which may be divided by a group, an amide group or an ether group, and which may be substituted with a hydroxy group. R ² , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group or a hydroxyethyl group. Z ⁻ is an anion, preferably a halogen ion, a sulfate ion, a fatty acid ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]

In addition, the organic peracid produced from the bleach activator is sterilizing in laundry systems and has the effect of reducing the number of living microorganisms remaining in clothing (Yukitaka Miyamae, Satoshi Matsunaga, Seiichi Tobe, Takahashi) Kenji, Haruo Yoshimura, Teruhisa Uzuki, Abstracts of the 28th Symposium on Cleaning, p.157-165 (1996)). From the viewpoint of sterilizing power, a bleach activator that generates a C8 to C12 organic peracid is particularly preferable. Specific examples of these bleach activators include decanoyloxybenzoic acid, sodium dodecanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, and the like. Among them, 4-decanoyloxybenzoate is preferred in terms of bleaching effect. Acid, sodium 4-nonanoyloxybenzenesulfonate is more preferred. From the viewpoint of the fading inhibiting effect, 4-decanoyloxybenzoic acid and sodium 4-dodecanoyloxybenzenesulfonate are preferable.
In the present invention, the bleach activator is preferably blended as a granulated product or molded product from the viewpoint of storage stability during storage.

≪Perfume≫
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 | flavor composition is a mixture which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc. When mix | blending the said fragrance | flavor composition with the bleaching composition of this invention, the content is in a bleaching composition, Preferably it is 0.001-20 mass%, More preferably, it is 0.01-10 mass%.
When blending the above fragrance component with the powder bleaching composition of the present invention, the surfactant-containing particles or the finally obtained bleaching composition at the time of preparation of the surfactant-containing particles are mixed in a mixer. The fragrance component is preferably used by spraying or dripping, more preferably by spraying.

≪Dye≫
Various dyes can be used to improve the appearance of the bleaching composition. Examples of the coloring matter used in the bleaching composition include dyes and pigments. Among them, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance such as oxides are particularly preferable. Preferred compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, bitumen, cyanine blue, cyanine green and the like. Further, these dyes are preferably granulated together with the catalyst body. In this case, it is preferable to use those obtained by dissolving or dispersing the dye in a binder compound such as polyethylene glycol (PEG).

≪Fluorescent whitening agent≫
In the bleaching composition of the present invention, as a fluorescent dye, for example, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -Biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative, bis- (triazinylaminostilbene) disulfonic acid derivative and the like. Commercially available fluorescent dyes include Whiteex SA, Whiteex SKC (trade name; manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba Specialty) Chemicals), Lemonite CBUS-3B (trade name; manufactured by Khyati Chemicals) and the like. Among these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable, and the content is preferably 0.001 to 1% by mass. These may be used alone or in combination of two or more.

≪Enzyme≫
Enzymes that can be incorporated into the bleaching composition include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified according to the reactivity of the enzyme. it can. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.
Examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. As commercial products of protease, sabinase, alcalase, cannase, everase, deozyme (above, trade name: manufactured by Novozymes); API21 (trade name: manufactured by Showa Denko KK); Maxacar, Maxapem (above, trade name: Genencor) Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.

Examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposome (trade name; manufactured by Showa Denko KK).
As cellulase, cellzyme (trade name; manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E-III (and above) And cellulase described in JP-A-63-264699).
Examples of the amylase include commercially available stainzymes, termamyls, duramils (above, trade names: manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

≪Enzyme stabilizer≫
The bleaching composition of the present invention can contain calcium salts, magnesium salts, polyols, formic acid, boron compounds and the like as enzyme stabilizers. In these, sodium tetraborate, calcium chloride, etc. are more preferable, and as content, 0.05-2 mass% is preferable in a composition. These may be used alone or in combination of two or more.

≪Other polymers≫
Polyethylene glycol having an average molecular weight of 200 to 200,000 or a weight average molecular weight of 1000 to 1000 as a binder or a powder preparation in the case of increasing the density of active agent-containing particles, and further to impart an anti-recontamination effect on hydrophobic fine particles. 100000 acrylic acid and / or maleic acid polymers, cellulose derivatives such as polyvinyl alcohol and carboxymethyl cellulose can be blended. Moreover, in order to mix | blend the copolymer or terpolymer of a terephthalic acid and ethylene glycol and / or a propylene glycol unit etc. as a soil | polishing agent, and in order to provide a color transfer prevention effect, polyvinylpyrrolidone etc. can be mix | blended. Among these, polyethylene glycol having an average molecular weight of 1500 to 7000 is preferable, and the content is preferably 0.05 to 5% by mass. These may be used alone or in combination of two or more.

≪Anti-caking agent≫
As an anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

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

≪Reducing agent≫
Examples of the reducing agent include sodium sulfite and potassium sulfite.

≪Metal ion scavenger≫
The metal ion scavenger captures trace metal ions and the like in tap water, and has an effect of suppressing adsorption of metal ions to fibers (objects to be cleaned).
Examples of metal ion scavengers that can be incorporated into the bleaching composition include aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and glycolethylenediaminehexaacetic acid; Ethane-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-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylene Phosphonic acid), diethylenetriaminepenta (meth) Nhosuhon acid) organic phosphonic acid derivative or a salt thereof and the like; diglycolic acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
It is necessary to consider that the content of the metal ion scavenger in the bleaching composition is used within a range that does not impair the performance of the catalyst body.

≪pH adjuster≫
The pH of the bleaching composition is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by weight aqueous solution of the bleaching composition is preferably 8 or more, and in the 1% by weight aqueous solution, More preferably, the pH is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the bleaching composition, the pH is usually adjusted with an alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, and the like. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.
Moreover, in order to prevent that pH of a bleaching composition becomes high too much, it can also adjust to the said pH range using an acid etc.
Examples of such acids include the metal ion scavengers, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, sodium hydrogen carbonate, sulfuric acid, Hydrochloric acid or the like can be used.
Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

(Method for producing bleaching composition)
The manufacturing method of a bleaching composition is not specifically limited, It can determine according to the form of the desired bleaching composition. Examples of the form of the bleaching composition of the present invention include solids such as powders, granules, tablets, briquettes, sheets or bars, and it is preferable to apply the present invention to the powder bleaching composition. As a manufacturing method of a bleaching composition, the manufacturing method which mixes (A) component mentioned above, surfactant-containing particle | grains, and (C) component using a powder mixer, and is set as the bleaching composition of a powder. Can be mentioned. Or the manufacturing method which uses (A) component, surfactant containing particle | grains, and (C) component as a tablet using a tableting machine is mentioned.

  Although the physical property value of the finally obtained bleaching composition is not particularly limited, the bulk density is usually 0.3 g / mL or more, preferably 0.4 to 1.2 g / mL, more preferably. Is 0.5 to 1.0 g / mL. The average particle diameter is preferably 200 to 1500 μm, more preferably 300 to 1000 μm. When the thickness is less than 200 μm, dust may be easily generated. On the other hand, when the thickness exceeds 1500 μm, the solubility may be insufficient. Further, the fluidity of the surfactant-containing particles is preferably 60 ° or less, particularly 50 ° or less as an angle of repose. If it exceeds 60 °, the handleability of the particles may deteriorate.

(How to use bleaching composition)
The method of using the bleaching composition of the present invention is not particularly limited. For example, in the case of a bleaching composition, the bleaching composition is charged to 0.02 to 0.5% by mass in the cleaning liquid, A method such as washing the object to be cleaned in a washing machine or immersing the object to be cleaned in a cleaning solution having a bleaching agent concentration of 0.02 to 2% by mass is preferable. Especially, the immersion time is 15 minutes. It can be suitably used for soaking for about 12 hours, preferably about 15-60 minutes. Further, for example, in the case of a detergent composition, the detergent composition is added to the cleaning solution so that the detergent composition becomes 0.02 to 2% by mass, and the washing object is washed in a washing machine, or the concentration of the detergent composition is 0.02. A method of immersing an object to be cleaned in a cleaning liquid of ˜2% by mass is suitable, and it can be suitably used for washing in a washing machine for 5 to 20 minutes.

As described above, the bleaching composition of the present invention comprises a component (A) and a component (b) and / or a reaction product as a catalyst, and the catalyst (C) is coated with the component (A). : Coated catalyst body, (B) component: surfactant, (C) component: peroxide, can prevent discoloration of the object to be washed and generation of off-flavor during storage, and has excellent bleaching effect It can be demonstrated.
In recent years, drum type washing machines have become widespread, and the washing time is about 1.5 to 2 times that of conventional vertical washing machines. For this reason, considering the interaction between the surfactant and hydrogen peroxide in the cleaning liquid, it is necessary to keep the hydrogen peroxide concentration in the cleaning liquid high for a long time in order to obtain a good bleaching effect (function). In the present invention, the complex can be more stably maintained in the cleaning liquid by selecting the component (a) having a relatively high coordination constant as the compound that forms a complex with the component (b) in the cleaning liquid. Even in long-term washing in a drum-type washing machine, the hydrogen peroxide concentration in the washing liquid can be kept high, and a good bleaching effect can be exhibited.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, it is not limited to an Example. Note that “%” indicates “% by mass” and “parts” indicates “parts by mass” unless otherwise specified.

(Evaluation methods)
<Evaluation of catalyst body coverage>
≪Test method≫
The catalyst body coverage was evaluated by the following method. Regarding the catalyst granules in Examples 1 to 16 and Comparative Examples 1, 8, and 9 below, the surface of component (A) was observed using a scanning electron microscope (supplied by Shimadzu Corporation, SUPERSCAN SS-550). It was. Using the still image analysis software, the area where the component (c) is attached is calculated by image processing, and the area ratio of the component (c) to the area of the catalyst body in the image is calculated. The coverage was calculated.

≪Evaluation method≫
A: Catalyst body coverage 90% or more B: Catalyst body coverage 80% or more and less than 90% C: Catalyst body coverage 60% or more and less than 80% D: Catalyst body coverage 40% or more and less than 60% E: Catalyst body coverage Less than 40%

<Evaluation of the amount of residual hydrogen peroxide>
≪Test method≫
The amount of residual hydrogen peroxide was evaluated by the following method. A sample of the cleaning solution was prepared by dissolving in 900 mL of tap water having a water temperature of 15 ° C. so that each bleaching composition in each example had a concentration of 667 mg / L. Subsequently, assuming a use environment, stirring is performed for 10 minutes at 120 rpm and 15 ° C. using a Terg-O-Tometer (manufactured by U.S. Testing), and the effective oxygen concentration of the sample before and after the stirring process (Hereinafter AVO) (%) was measured. The residual hydrogen peroxide was measured by obtaining AVO by an iodometry method.
First, 900 mL of the sample before or after the stirring treatment was put in a 2 L beaker, 10 mL of 33% acetic acid aqueous solution was added, and then 5 mL of 10% potassium iodide solution (first grade, manufactured by Junsei Chemical Co., Ltd.) was added. While stirring with a magnetic stirrer, a few drops of 1% aqueous ammonium molybdate tetrahydrate solution (1st grade, manufactured by Junsei Chemical Co., Ltd.) was added, and then 0.1 mol / L sodium thiosulfate solution (produced by Junsei Chemical Co., Ltd.) Titration with. The end point was when the color of the solution became colorless from brown to yellow. The AVO was determined by the following formula (iii), and the residual hydrogen peroxide (%) in the sample 10 minutes after the following formula (iv) was determined with the effective oxygen concentration before the start of stirring as 100%.

 AVO (%) = {0.1 × f × titration (mL) × (1/2) × (1/1000) × 16} ÷ sample amount (g) × 100 (iii)

 [F: Potency of 0.1 mol / L sodium thiosulfate]

  Residual hydrogen peroxide (%) = AVO (%) of the sample after the stirring treatment ÷ AVO (%) of the sample before the stirring treatment × 100 (iv)

≪Evaluation method≫
From the above formulas (iii) and (iv), determination was made from the calculated residual hydrogen peroxide according to the following evaluation criteria.
A: 70% or more B: Over 40%, less than 70% C: 40% or less

<Evaluation of odor control effect>
≪Test method≫
The bad odor control effect was tested by the following method. Bleaching compositions having the compositions of the following examples and comparative examples in plastic sealed containers (S-22, dimensions: 167 mm × 117 mm × 58 mm, main body material: polypropylene, lid material: EVA resin, manufactured by Entec Co., Ltd.) Enclose 0.5 kg, perform accelerated test of off-flavor generation for 3 weeks under the recycling conditions of 45 ° C, 85% humidity, 16 hours → 25 ° C, 65% humidity, 8 hours, sensory odor of bleaching composition Evaluation was performed.

≪Evaluation method≫
The evaluation of the off-flavor suppression effect was performed by an expert in accordance with the following 6-step odor intensity labeling method and sensoryly evaluating the odor of the bleaching composition after storage.
0: Odorless 1: Smell that can be finally detected 2: Smell that understands what odor is 3: Smell that can be easily detected 4: Strong odor 5: Strong odor

<Evaluation of the effect of inhibiting discoloration>
≪Test method≫
The haze discoloration suppressing effect was tested by the following method. Place a blue polo shirt cloth (6cm x 6cm, UNIQLO Heavyweight T-shirt (short sleeve) 65Blue) on a plastic petri dish, and uniformly sprinkle 2.5g of the bleaching composition of the composition of Examples and Comparative Examples on it, I covered another same blue polo shirt cloth. 4 mL of 40 ° C. tap water was dropped on the entire blue polo shirt cloth, and the petri dish lid was closed and allowed to stand for 120 minutes. After leaving still for 120 minutes, the bleaching composition adhering to the blue polo shirt cloth was washed away, and a normal course (rinsing twice tap water) of a washing machine (JW-Z23A type, manufactured by Haier) was performed and dried with an iron.

≪Evaluation method≫
The discoloration after drying with an iron was visually compared and judged according to the following evaluation criteria.
○: No discoloration compared to untreated product ×: Discoloration observed compared to untreated product

(Raw material)
The raw materials used in the examples and comparative examples are as follows.
<Component (A): Coated catalyst body>
<< (a) component: chelate compound >>
HIDS: 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt (manufactured by Nippon Shokubai Co., Ltd.)
IDS: 2,2′-iminodisuccinic acid tetrasodium salt (manufactured by LANXESS)
MGDA: methyl glycine diacetic acid trisodium salt (manufactured by BASF)

≪ (a ′) component: Comparative product of component (a) ≫
DPA: 2-6-pyridinecarboxylic acid (manufactured by ACROS ORGANICS)

<< (b) component: copper compound and / or manganese compound >>
・ Copper (II) sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.)
Manganese chloride (MnCl ₂ ) tetrahydrate (reagent, manufactured by Kanto Chemical Co., Inc.)

<< (c) component: water-insoluble inorganic powder >>
Aluminosilicate A-type zeolite a: SP # 2300 (average particle size: 1.25 μm, manufactured by Nitto Flour Chemical Co., Ltd.)
Aluminosilicate A-type zeolite b: VALFOR 100 zeolite NaA (average particle size: 4 μm, manufactured by PQ Chemical Co.)
・ Aluminosilicate A-type zeolite c: Zeolite 4A (average particle size: 7 μm, manufactured by SHANDONG ALMINIUM)
Aluminosilicate A-type zeolite d: Nitto zeolite # 150 (average particle size: 100 μm, manufactured by Nitto Flour Chemical Co., Ltd.)
Bentonite N-type montmorillonite (Kunipia F, average particle size: 100 μm, Kunipia Industries Co., Ltd.)
・ Titanium oxide (ST01, average particle size: 7 nm, manufactured by Ishihara Sangyo Co., Ltd.)

<< (c ') Component: Powder not belonging to (c) Component >>
・ Water-soluble inorganic powder: Sodium sulfate Neutral anhydrous sodium sulfate (neutral anhydrous sodium sulfate A0B, average particle size: 150 μm, manufactured by Shikoku Kasei Co., Ltd.)
Water-soluble organic powder: powdered cellulose (KC Flock, W-400G, average particle size: 24 μm, manufactured by Nippon Paper Chemicals Co., Ltd.)

≪Binder compound≫
PEG 6000: polyethylene glycol # 6000M (average molecular weight 8300, freezing point 58 degrees, manufactured by Lion Corporation)

<(B) component: Surfactant and optional component>
In Examples and Comparative Examples, particles prepared as surfactant-containing particles containing the component (B) according to the formulation shown in Table 1 were used. The following abbreviations in Table 1 were used.
≪Surfactant≫
MES: sodium salt of fatty acid methyl ester sulfonate having 16 carbon atoms: 18 carbon atoms = 80: 20 (manufactured by Lion Corporation, AI = 70%, the remainder being unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, excess Hydrogen oxide, water, etc.)
LAS salt: Compound obtained by neutralizing linear alkyl (C10-14) benzenesulfonic acid (Lypon LH-200 (LAS-H pure 96%) manufactured by Lion Corporation) with 48% aqueous sodium hydroxide during preparation What mixed (LAS-Na) and the compound (LAS-K) neutralized with 48% potassium hydroxide aqueous solution instead of sodium hydroxide by mass ratio 2: 1. The blending amount in the table indicates a value (mass%) as a mixture of these. Soap: sodium fatty acid having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid Composition: C12: 11.7%, C14: 0.4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid) : 1.2%, molecular weight: 289)
Nonionic surfactant: ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN) adduct with an average of 15 moles of ethylene oxide << optional component >>
・ Sodium carbonate: Heavy sodium carbonate (soda ash, manufactured by Asahi Glass Co., Ltd.)
・ Fluorescent whitening agent: Chino Pearl CBS-X (Ciba Specialty Chemicals)
Enzyme: Mixture of Evalase 8T (Novozymes) / LIPEX50T (Novozymes) / Termamyl 60T (Novozymes) / Celzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) Polymer A: Sodium salt of acrylic acid / maleic acid copolymer (trade name: Socaran CP7, manufactured by BASF)
Fragrance: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18]
CMC: Carboxymethylcellulose (trade name: CMC Daicel 1190, molecular weight: 820,000, degree of etherification: 0.7, manufactured by Daicel Chemical Industries, Ltd.)

<(C) component: peroxide>
-Percarbonate 1: Coated sodium percarbonate coated with silicic acid and sodium borate (trade name: SPC-D, effective oxygen amount 13.2%, average particle size: 760 μm, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
Percarbonate 2: Sodium percarbonate (trade name: SPCC, effective oxygen content: 13.8%, average particle size (mass 50%): 870 μm, manufactured by Zheanji JINKE CHEMICALS)
-Percarbonate 3: Blend product of sodium percarbonate / sodium carbonate / sodium bicarbonate = 77/3/20 (trade name: SPC-Z, effective oxygen content: 10.9%, average particle size: 500 μm, Mitsubishi Gas Chemical Co., Ltd.)

Production Example 1 Production of Surfactant-Containing Particle Composition According to the composition shown in Table 1, a surfactant-containing particle composition was produced by the preparation method shown below.
Step (A): Water was placed in a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, a surfactant excluding MES and nonionic surfactant was added and stirred for 10 minutes. Subsequently, MA agent (acrylic acid / maleic acid copolymer sodium salt) was added. After further stirring for 10 minutes, a part of A-type zeolite a (1.0% for addition at the time of kneading, 5.0% for grinding aid, 1.5% of the surface from the addition amount described in Table 1) Sodium carbonate was added in an amount excluding the A-type zeolite a for reforming). After further stirring for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, spray drying was performed using a countercurrent spray drying tower at a hot air temperature of 280 ° C., and the average particle size (mass 50%): 320 μm, Spray-dried particles having a bulk density of 0.30 g / cm ³ and a water content of 5% were obtained.

  Step (B): Spray-dried particles obtained in step (A), MES, 1.0% A-type zeolite a, remaining nonionic surfactant excluding 0.5% nonionic surfactant for spray addition, fluorescence Whitening agent, polymer A and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Co., Ltd.) and kneaded under conditions of kneading capacity: 120 kg / hr, temperature: 60 ° C., and surface activity A 6% water mixture containing the agent was obtained.

  Step (C): The mixture obtained in Step (B) is extruded with a pelleter double (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) equipped with a die having a hole diameter of 10 mm and cut with a cutter (cutter (Peripheral speed: 5 m / s) A pellet having a length of about 5 to 30 mm was obtained. Next, Fitzmill (DKA-3, Hosokawa Micron) was added to the obtained pellets by adding 5.0% of A-type zeolite a as a grinding aid and arranged in series in the presence of cold air (10 ° C., 15 m / s). Co., Ltd.) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage are all 4700 rpm) A surfactant-containing particle was obtained.

Step (D): The surfactant-containing particles obtained in Step (C) and the CMC are placed in a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, inside the drum inner wall surface of the container 131.7 L). A type zeolite a for surface modification of 1.5% under the conditions of a clearance of 20 mm and a baffle plate with a height of 45 mm and a filling rate of 30% by volume, a rotational speed of 22 rpm and 25 ° C. And sprayed with 0.5% nonionic surfactant and fragrance to roll for 1 minute to obtain surface-modified particles.
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) Under the conditions of volume%, rotation speed 22 rpm, and 25 ° C., the particles obtained above and the enzyme were added and mixed for 5 minutes to obtain a surfactant-containing particle composition.

(Manufacture example 2) Manufacture of catalyst granulations 1-3, 5-13 According to the mixing | blending of Table 2, the catalyst granulations 1-3, 5-13 which are coating catalyst bodies were manufactured with the following method.
<Molding process>
The mixed powder of component (a), component (b) and binder component is put into a continuous kneader (KRS-S1 type, manufactured by Kurimoto Iron Works Co., Ltd.), kneaded at 60 ° C., and extruded through a 1 mm porous screen. A noodle-like mixture was obtained. The obtained mixture was pulverized using a pulverizer (NEW SPEED MILL, manufactured by Okada Seiko Co., Ltd.) to obtain a pulverized product. The pulverized product was sieved to obtain a catalyst body having a particle size of 300 to 700 μm.

<Coating process>
In accordance with Table 2, the obtained catalyst body and the component (c) were mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, the inner wall surface of the drum of the container 131.7L, the clearance between the inner wall surface 20 mm, high 2 pieces of baffle plates having a thickness of 45 mm), and tumbled and mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C. -3, 5-13 were obtained. The amount of component (c) added is “parts” added to 100 parts of the catalyst body.

(Production Example 3) Production of catalyst granulated product 4 According to the formulation shown in Table 2, 1.0 g of copper (II) sulfate pentahydrate and 16 g of MGDA were added to 300 ml of ion-exchanged water and stirred at room temperature for 10 minutes. did. Thereafter, water is distilled off under reduced pressure on an oil bath maintained at 150 ° C., and the dried solid is recovered, whereby a complex of methyl glycine diacetate and methyl glycine diacetate (MGDA-Cu) is a catalyst. As a result, the same molding process as in Production Example 2 was performed. The obtained catalyst body was treated in the same manner as in the coating step of Production Example 2 to obtain a catalyst granulated product 4 as a coated catalyst body. In Table 2, the complex (MGDA-Cu) is shown in the column of the component (a).

(Manufacture example 4) Manufacture of catalyst granule 14-14,19 According to the mixing | blending of Table 2, catalyst granule 14-17,19 was manufactured like manufacture example 2 except not having provided the coating process. .

(Manufacture example 5) Manufacture of the catalyst granulated material 18 According to the mixing | blending of Table 2, the catalyst granulated material 18 was manufactured like the manufacture example 3 except not having provided the coating process. In Table 2, the complex (MGDA-Cu) is shown in the column of the component (a).

(Manufacture example 6) Manufacture of catalyst granulated material 20 and 21 According to the mixing | blending of Table 2, (c) component was made into the component (c ') component (sodium sulfate or powdered cellulose) similarly to manufacture example 2, and a catalyst Granulated materials 20 and 21 were produced.

(Production Example 7) Production of coated copper sulfate To 2.5 parts of copper sulfate, 97.5 parts of binder compound and 14 parts of A-type zeolite a as component (c) were put into a horizontal cylindrical rolling mixer, and the filling rate Coated copper sulfate was produced by rolling and mixing for 1 minute under the conditions of 30% by volume, 22 rpm, and 25 ° C.

(Production Example 8) Production of coated MGDA For 40 parts of MGDA, 60 parts of binder compound and 14 parts of A-type zeolite a as component (c) were put into a horizontal cylindrical rolling mixer, filling rate 30 volume%, rotation speed 22 rpm The coated MGDA was produced by rolling and mixing for 1 minute at 25 ° C.

(Examples 1-16, Comparative Examples 1-9)
According to the composition of Tables 3 and 4, the catalyst granulated product, the percarbonate, and the surfactant-containing particle composition were mixed to obtain a bleaching composition. About the obtained bleaching composition, evaluation of the above-mentioned strange odor suppression effect and a discoloration suppression effect and evaluation of residual hydrogen peroxide were performed, and the results are shown in Tables 3 and 4.

(Comparative Example 10)
According to the formulation of Table 4, coated copper sulfate, coated MGDA, percarbonate and surfactant-containing particles were mixed to obtain a bleaching composition. About the obtained bleaching composition, evaluation of the above-mentioned strange odor suppression effect and a discoloration suppression effect and evaluation of residual hydrogen peroxide were performed, and the result is shown in Table 4.

As shown in Tables 3 and 4, Examples 1 to 16 using the coated catalyst particles in which the catalyst body was coated with the component (c): water-insoluble inorganic powder were excellent in the off-flavor suppressing effect and the discoloration suppressing effect. In addition, in Examples 3 and 14 to 16 in which only the average particle diameter of the component (c) is different, Examples 3, 14, and 15 in which the catalyst body was coated with A-type zeolite having an average particle diameter of less than 10 μm were The catalyst body coverage was higher than that of Example 16 in which the catalyst body was coated with A-type zeolite having a particle diameter of 100 μm, and the effect of suppressing odors was excellent. Further, in comparison between Example 3 and Example 9, Example 9 in which the catalyst body was coated with titanium oxide having an average particle diameter of less than 10 μm as component (c) showed an excellent off-flavor suppression effect, but the average particle The odor control effect was inferior to Example 3 in which the catalyst body was coated with an A-type zeolite having a diameter of less than 10 μm. In all the examples, the amount of residual hydrogen peroxide was 70% or more, which was sufficient for bleaching.
On the other hand, as shown in Table 4, Comparative Example 1 was excellent in the off-flavor suppression effect and browning suppression effect. However, the amount of residual hydrogen peroxide was as low as 40% or less. Although the comparative examples 2-7 which did not coat | cover the catalyst body were excellent in the discoloration discoloration suppression effect, they were inferior in the strange odor suppression effect. In addition, Comparative Example 8 coated with sodium sulfate, which is a water-soluble inorganic powder, and Comparative Example 9 coated with a water-soluble organic powder are excellent in the effect of suppressing discoloration, but have a catalyst body coverage of less than 60%. It was low and it was inferior to the off-flavor suppression effect. Further, Comparative Example 10 in which the component (a) and the component (b) were not granulated but separately coated with the component (c) was added, but the catalyst body coverage was high and the odor control effect was excellent. In addition, it was inferior in the effect of suppressing discoloration.
From the above results, it was found that the bleaching composition of the present invention can prevent discoloration of the object to be cleaned and generation of a strange odor during storage, and is excellent in the bleaching effect.

Claims (2)

(A) component: a catalyst body containing a mixture and / or a reaction product of a chelate compound selected from aminocarboxylic acids represented by the following general formulas (I) and (II) and at least one of a copper compound and a manganese compound A coated catalyst body coated with a water-insoluble inorganic powder;
(B) component: surfactant,
(C) Ingredient: A bleaching composition containing a peroxide.

(In Formula (I), Z ^{1 to} Z ⁴ each independently represent COOX ¹ , an alkyl group having 1 to 30 carbon atoms, a sulfo group, or an amino group, and at least one of Z ^{1 to} Z ⁴ is COOX ¹ . X ¹ independently represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom, R represents a hydrogen atom or a hydroxyl group, Q represents a hydrogen atom or an alkyl group, and n ₁ represents , Represents an integer of 0 or 1.)

(In Formula (II), Y represents an alkyl group, a carboxyl group, a sulfo group, an amino group, a hydroxyl group, or a hydrogen atom. Z ^{5 to} Z ⁷ are each independently, COOX ² , a hydrogen atom having 1 to 30 carbon atoms, and hydrogen. Represents an alkyl group, a sulfo group, or an amino group in which a part of the atoms may be substituted, and at least one of Z ^{5 to} Z ⁷ is COOX ^2. X ² is independently a hydrogen atom or an alkali metal And represents an alkaline earth metal atom and a cationic ammonium group, and n ₂ represents an integer of 0 to 5.)   The bleaching composition according to claim 1, wherein the water-insoluble inorganic powder is A-type zeolite.